Unsaturated peroxide compositions, polymeric-peroxides derived therefrom and their uses

ABSTRACT

Novel unsaturated peroxide compositions of Structure A, 
     
         R--Q--X--R.sub.1                                           A 
    
     [Where the R--Q-- grouping contains a polymerizable carbon-carbon double bond, --X-- is a direct bond or a connecting diradical and --R 1  is a peroxide containing radical all as defined in the Summary of the Invention Section.], polymeric-peroxide compositions derived from them and their uses are disclosed.

"This is a divisional of application Ser. No. 08/196,339 filed on Feb.9, 1994 now U.S. Pat. No. 5,475,072."

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel unsaturated peroxides, their use asfree-radical generators for, (1) polymerizing ethylenically unsaturatedmonomers, (2) curing unsaturated polyester resins, (3) crosslinkingolefin polymers, (4) preparing polymeric peroxides, (5) curingelastomeric compositions, (6) rheological modification of olefinpolymers and copolymers, (7) grafting of ethylenically unsaturatedmonomers onto polymers, and (8) compatibilizing of polymer blends.Compounds and processes for their preparation as well as products andarticles of manufacture produced by their use are also contemplated bythe invention.

There is a need in the polymer industry for efficient, free-radicalcrosslinking agents for olefin polymers which give longer scorch timesand yet provide faster crosslinking rates. Because of its low melt flow,HDPE must be compounded with peroxides at temperatures where the scorchtime is relatively short. If the scorch time is too short, prematurecrosslinking of HDPE occurs during the peroxide compounding step. Thisis highly undesirable. In the crosslinking of high density polyethylene(HDPE), the peroxide that is predominantly used for crosslinking is2,5-dimethyl-2,5-di-(t-butylperoxy)-3-hexyne (available as LUPERSOL® 130from Elf Atochem North America, Inc.). Of all the commercially availableorganic peroxides, LUPERSOL 130 has the highest 10 hour half-lifetemperature (131° C.). The 10 hour half-life temperature of an initiatoris defined as the temperature at which 50% of the initiator decomposesin 10 hours. Generally, the higher the 10 hour half-life temperature thelonger the scorch time at a given temperature.

Although LUPERSOL 130 gives adequate scorch times when compounded intoHDPE, polymer producers complain of the noxious decomposition productsthat LUPERSOL 130 produces during crosslinking of polyethylene. Thenoxious decomposition products are thought to be derived from thecarbon-carbon triple bond in LUPERSOL 130 since a similar peroxide thatlacks the carbon-carbon triple bond,2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, does not produce noxiousdecomposition products. An efficient polyethylene crosslinking agentwhich yields lengthened scorch times and produces less noxiousdecomposition products is needed by the polyethylene crosslinkingindustry.

A novel unsaturated peroxide of the instant invention,1,3-dimethyl-3-(t-butylperoxy)butyl methacrylate, satisfied thesecrosslinking needs and was found to be a more effective HDPEcrosslinking agent than was LUPERSOL 130. At 385° F. (196° C.) in HDPE,1,3-dimethyl-3-(t-butylperoxy)butyl methacrylate was found to be atleast as efficient as LUPERSOL 130 on an equivalent basis and was foundto give faster crosslinking of HDPE than LUPERSOL 130. It also gavelonger scorch times than LUPERSOL 130, hence, it is superior to LUPERSOL130 for crosslinking of HDPE. Perhaps because of the lack of acarbon-carbon triple bond in the structure of1,3-dimethyl-3-(t-butylperoxy)butyl methacrylate, generation of noxiousdecomposition products during crosslinking of polyethylene was notobserved.

In recent years most of the new polymeric materials that have beencommercialized are polymeric blends and alloys composed of two or moredifferent polymers. The reasons for this trend to commercial developmentof polymer blends and alloys include the short time required fordevelopment and commercialization of these materials, the relatively lowcost involved in carrying out the R&D effort needed to develop thesematerials compared to development of entirely new polymers frommonomers, and the ability to develop polymeric blends and alloys thatare "tailor made" to meet end use property specifications, hence, theyare neither over-engineered nor under-engineered, but are just right.

The polymer property improvements achieved by blending include:

Better processability

Impact strength enhancement

Improved flame retardance

Improved barrier properties

Improved tensile properties

Improved adhesion

Improved melt flow

Enhanced heat distortion temperature (HDT)

Enhanced heat resistance

Improved stiffness

Improved chemical resistance

Improved ultraviolet light stability

The major problem encountered in developing new blends and alloys is theinherent incompatibility or immiscibility of almost all mixtures of twoor more polymers. The consequence of incompatibility of polymeric blendsand alloys is that they are unstable and, with sufficient time andtemperature, form separate phases, thus, physical properties of thepolymeric blends and alloys suffer. Generally, resin compounders havefound that block and graft copolymers having polymeric segments that arecompatible with the individual polymer components of blends and alloysenable formation of blends and alloys having enhanced phase stabilitiesand physical properties.

Low cost blends and alloys are commercially produced from two or moreaddition polymers such as blends involving low density polyethylene(LDPE), linear low density polyethylene (LLDPE), high densitypolyethylene (HDPE) and polypropylene (PP). The compatibility of theselow cost blends can be improved by crosslinking with peroxides or by useof compatibilizing block or graft copolymers as mentioned above.

An important use of polymeric-peroxides such as polymers derived fromthe novel unsaturated peroxides of Structure A (as defined herein below)is their utility in preparing graft copolymers useful forcompatibilizing polymeric blends and alloys. The polymeric-peroxides,derived from the novel unsaturated peroxides of Structure A of theinstant invention, are effective in the preparation of graft copolymercompositions. Such graft copolymers have utility in compatibilizingpolymer blends and alloys.

2. Discussion of Prior Art

U.S. Pat. No. 4,119,657 discloses OO-t-alkyl O-allyl and O-methallylmonoperoxycarbonates: ##STR1##

Later publications, Chem. Abstracts, 91, 58075y, abstracting Japanesekokai 79 47,790; Chem. Abstracts, 92, 129658z, abstracting Japanesekokai 79 132,695; Chem. Abstracts, 92, 130797a, abstracting Japanesekokai 79 142,239; and Chem. Abstracts, 93, 48080y, abstracting Japanesekokai 80 09636 disclose preparations of polymeric peroxides bycopolymerizing these OO-t-alkyl O-allyl and O-methallylmonoperoxycarbonates with ethylenically unsaturated monomers andpreparations of graft copolymers from the resulting polymeric peroxides.These peroxides and the polymeric peroxides derived from them are notcovered by the novel unsaturated peroxides of Structure A and thecorresponding novel polymeric-peroxides derived from the compositions ofStructure A.

F. Strain, J. Am. Chem. Soc., 72, pp. 1254-1263 (1950) disclosed lowtemperature dialkyl peroxydicarbonates and reported the preparation ofdiallyl peroxydicarbonate, a peroxydicarbonate with allyl groups. Basedon data in this paper the latter peroxydicarbonate was very hazardousand exploded.

Chem. Abstracts, 79, 6548n, abstracting Italian Patent 869,166 disclosesunsaturated diperoxide compounds for vulcanization of ethylene-propylenerubber, such as 1-phenyl-3,3-di-(t-butylperoxy)-1-propene: ##STR2##

The latter is not expected to polymerize very readily owing to thepresence of a substituent on each of the unsaturated carbons. Thestructures of this Italian Patent are not covered by Structure A of theinstant invention.

U.S. Pat. No. 3,536,676 discloses di-t-alkyl diperoxyfumarates and thecopolymerizations of these diperoxyfumarates with monomers such asstyrene, vinyl acetate, vinyl chloride, acrylonitrile, methylmethacrylate and butadiene.

U.S. Pat. No. 3,763,112 discloses the preparations of di-t-alkyldiperoxyfumarate adducts (polymeric and non-polymeric) that arepreparable via reaction of di-t-alkyl diperoxyfumarate with compoundspossessing labile C--H bounds, in the presence or absence ofconventional free-radical generators and or upon exposure to actiniclight (visible, ultraviolet, etc.).

Chem Abstracts, 105(20), 173232s, abstracting Japanese PatentApplication 84/209679 discloses various OO-t-alkyl O-alkylmonoperoxyfumarates and the use of these monoperoxyfumarates in thepreparation of styrene polymers of enhanced moldability.

British Patent 1,041,088 discloses peroxide-containing copolymercompositions derived from ethylenically unsaturated monomers such asvinyl esters, esters of (meth) acrylic acid, vinyl chloride,acrylonitrile, butadiene, isoprene, acrylamide and vinyl ethers, andunsaturated peroxyesters such as t-butyl peroxymethacrylate, OO-t-butylO-hydrogen monoperoxymaleate, OO-t-butyl O-butyl monoperoxymaleate,OO-t-butyl O-butyl monoperoxyfumarate and t-butyl peroxycinnamate. Inthe cases of the OO-t-alkyl O-hydrogen monoperoxy fumarates and theOO-t-alkyl O-hydrogen monoperoxymaleates, polymers produced from themare expected to react at elevated temperatures via non-radical reactionsto form non-peroxidic polymers and t-alkyl hydroperoxides. t-Butylperoxymethacrylate is difficult to prepare and is hazardous owing tovery exothermic self polymerization/decomposition. t-Butylperoxycinnamate does not homopolymerize nor copolymerize very readilywith common polymerizable ethylenically unsaturated monomers.

U.S. Pat. No. 4,658,001 discloses polymerizable, ethylenicallyunsaturated monoperoxycarbonates of Structure Z. ##STR3## and copolymersderived therefrom. Peroxide compounds of Structure Z are not covered bythe unsaturated peroxide compositions of Structure A.

U.S. Pat. No. 4,855,428 discloses triazine peroxides possessing at leastone carbon-carbon double bond, for instance,2-t-amylperoxy-4,6-dialloxy-1,3,5-triazine, which are useful forcrosslinking polymers and copolymers derived from ethylene. Thesecompositions are not covered by Structure A of the instant invention andare not expected to polymerize very readily.

U.S. Pat. Nos. 4,129,700, 4,180,518, and 4,218,548 claim peroxides ofthe general formula: ##STR4## where R₁ is hydrogen or an alkyl radicalof 1 to 4 carbons, R₂ and R₃ are alkyl radicals of 1 to 4 carbons, R₄ isa t-alkyl radical of 4 to 8 carbons, and Z is, ##STR5## where R₅ and R₇are alkyl radicals of 1 to 8 carbons, R₆ and R₈ are hydrogen, alkylradicals of 1 to 8 carbons, cycloalkyl radicals of 5 to 6 carbons,phenyl radicals, or alkylphenyl radicals of 7 to 10 carbons, and where Dis an ethynyl diradical, a diethynyl diradical, or an alkyl diradicalhaving 1 to 8 carbons. An example of a peroxide covered under thesepatents would be the reaction product of2-(t-butylperoxy)-2-methyl-4-hydroxypentane with cyclohexyl isocyanate.This compound does not have a pendent polymerizable vinyl group.Moreover, as can be seen from the general structure given by thesepatents, in no case is there a compound claimed with a pendentpolymerizable vinyl group as described by our general formula. However,another compound, whose synthesis is described in all three patents butwhich is not claimed, is the reaction product of allyl amine and2-(t-butylperoxy)-2-methyl-4-chlorocarbonyloxypentane, i.e.,N-allyl-O-[2-(t-butylperoxy)-2-methyl-4-pentyl]carbamate. Although thisperoxide contains an allyl group, it is outside the scope of ourinvention as described by our general formula, because for the abovecarbamate to be covered by the instant invention --X-- would have to bethe connecting diradical, --CH₂ NH--. This connecting diradical is notone of the definitions for --X-- of Structure A.

U.S. Pat. Nos. 3,671,651 and 4,304,882 broadly disclose polymers withattached peroxide groups. However, these peroxy polymers were producedby the reaction of a peroxychloroformate such as2-(t-butylperoxy)-2-methyl-4-chlorocarbonyloxypentane and a hydroxycontaining polymer such as a polyether diol (for example, Carbowax™produced by the Union Carbide Corp.). In general, U.S. Pat. No.3,671,651 teaches that a peroxide with an acylating functionality suchas an acid chloride or a chloroformate can react with polymerscontaining terminal or pendent hydroxyl, amino, and mercapto groups orany other functionality that can be acylated. This patent specificallyclaims peroxy polymers in which the peroxide is attached to the polymerby either an ester or a carbonate group (i.e. connecting groups), thereis no claim of either an amide, a carbamate, or a urea as connectinggroups which by definition are part of general structure A of ourinvention. Moreover, there is no mention that peroxy polymers can beprepared by copolymerization with a peroxy monomer. Therefore, theperoxy polymers of U.S. Pat. No. 3,671,651 are outside the scope of thisinvention. U.S. Pat. No. 4,304,882 also teaches that peroxides withacylating functionalities can react with polymers containing terminal orpendent hydroxyl, amino, or mercapto groups to form peroxy polymers. Inthis case amide and carbamate groups are specifically claimed asconnecting groups linking the peroxide moiety to the polymer backbone.However, there is no mention of vinyl group containing peroxy monomersbeing copolymerized with other monomers or of the peroxide being part ofthe repeat unit(s) in the polymer backbone. In addition there is adifference in the general formulas for this patent and our invention.The general formula for the peroxy polymers of U.S. Pat. No. 4,304,882is as follows:

    [A.sub.n1 --R--D.sub.n2).sub.v P.sub.n3 ].sub.v Z.sub.n4

where:

n1, n2, n3, n4, v, and w are integers; A defines a peroxide moiety; R isa di-, tri-, or tetra valent hydrocarbon radical; D is an ester,carbonate, amide, carbamate, etc. connecting group; P is a polyvalentresidue of a polymer less its terminal and pendent Z and (A_(n1)--R--D_(n2)) groups; and Z is --H, --OH, --NH₂, etc. Thus, in the caseof the general formula in U.S. Pat. No. 4,304,882, the --R--D-- groupconnects the peroxide unit, A-, to the polymer backbone. In the generalformula A for the compositions of the instant invention the connectinggroup between the polymer backbone and the peroxide group, --R₁, is--X--. The definitions of --X-- are different than those of --R--D. Forinstance, in the case of the peroxy-polymers of U.S. Pat. No. 4,304,882,the connecting group of atoms to the polymer backbone is either--O--(P)--, --NH--(P)--, --NR₂ --(P)-- or --S--(P)-- [Where (P) is apolymer backbone of U.S. Pat. No. 4,304,882.]. In the case of theinstant invention the connecting group of atoms to the polymer backboneis either one or more carbon atoms, --C(O)--(P')-- or --O--C(O)--(P')--[where (P') is a polymer backbone of the instant invention.] Thus, inthe instant invention the peroxide is attached to the polymer backboneby quite different connecting groups.

U.S. Pat. No. 5,011,981 discloses the reaction products of methacryloylisocyanate and hydroperoxides. A typical example is the reaction oft-butyl hydroperoxide with methacryloyl isocyanate to yield aperoxycarbamate with the following proposed structure: ##STR6## Althoughthis is a polymerizable peroxide, it is outside the scope of ourinvention, because for it to be included in our invention, --X-- of ourgeneral structure would have to be the connecting diradical,--C(O)--NH--. This connecting diradical is not included in thedefinition of --X--.

SUMMARY OF THE INVENTION

This invention provides in a first composition aspect novelethylenically unsaturated peroxide compositions of Structure A:

    R--Q--X--R.sub.1                                           A

where:

Q is an unsaturated diradical selected from structures (1), (2), or (3)##STR7## where (X--R₁) shows the point of attachment of the X--R₁ groupand (R) shows the point of attachment of the R group to the Q diradical;

R is selected from the group consisting of H--, carboxy, alkoxycarbonylradicals of 2 to 19 carbons, aryloxycarbonyl radicals of 7 to 15carbons, t-alkylperoxycarbonyl radicals of 5 to 11 carbons, alkylradicals of 1 to 18 carbons, alkenyl radicals of 2 to 18 carbons, arylradicals of 6 to 10 carbons, and R₁ --X-- radicals;

R₂ is selected from the group consisting of H-- and alkyl radicals of 1to 4 carbons;

R₃ is selected from the group consisting of H--, alkyl radicals of 1 to18 carbons and alkenyl radicals of 2 to 18 carbons provided that when R₃is methyl, R and R₂ are not both hydrogen;

R₁ is a peroxy containing radical of structures (4), (5), and (6):##STR8## where: t is 0 or 1;

v is 1 or 2;

w is 1 or 2;

T is a direct bond or oxy;

R₄ is selected from the group consisting of t-alkyl radicals of 4 to 12carbons, t-aralkyl radicals of 9 to 13 carbons and t-alkynyl radicals of5 to 9 carbons;

R₅, R₈ and R₉ are the same or different and are selected from the groupconsisting of alkyl radicals of 1 to 4 carbons; in structure (5) andwhen T is a direct bond in structure (6), R₆ and R₇ are the same ordifferent and are selected from the group consisting of H-- and alkylradicals of 1 to 4 carbons;

in structure (6) when T is oxy, R₆ and R₇ are the same or different andare selected from the group consisting of alkyl radicals of 1 to 4carbons;

R₁₀ is selected from the group consisting of t-alkyl radicals of 4 to 12carbons, t-aralkyl radicals of 9 to 13 carbons, t-alkynyl radicals of 5to 9 carbons, and structures (7), (8), (9), (11), (11) and (12):##STR9## where R₁₂ and R₁₃ can be the same or different and are selectedfrom the group consisting of H-- and alkyl radicals of 1 to 8 carbons;

R₁₄ is selected from the group consisting of H--, alkyl radicals of 1 to8 carbons, alkenyl radicals of 2 to 8 carbons, aryl radicals of 6 to 10carbons, alkoxy radicals of 1 to 6 carbons, and aryloxy radicals of 6 to10 carbons;

R₁₃ and R₁₄ may be concatenated to form an alkylene diradical of 4 to 5carbons;

R₁₅ and R₁₆ are independently selected from alkyl radicals of 1 to 4carbons;

R₁₇ and R'₁₇ are independently selected from the group consisting ofH--, lower alkyl radicals of 1 to 4 carbons, alkoxy radicals of 1 to 4carbons, phenyl radicals, acyloxy radicals of 2 to 8 carbons,t-alkylperoxycarbonyl radicals of 5 to 9 carbons, hydroxy, fluoro,chloro, and bromo;

x is 0 or 1;

R₁₈ is selected from substituted or unsubstituted alkyl radicals of 1 to18 carbons, substituents being one or more alkyl radicals of 1 to 6carbons, t-alkylperoxy radicals of 4 to 8 carbons, alkoxy radicals of 1to 6 carbons, aryloxy radicals of 6 to 10 carbons, hydroxy, chloro,bromo and cyano; substituted or unsubstituted cycloalkyl radicals of 5to 12 carbons, substituted or unsubstituted saturated heterocycles of 5to 12 atoms having an oxygen atom or a nitrogen atom in the heterocyclicring with substituents for either cyclic radical being one or more loweralkyl radicals of 1 to 4 carbons, or R₁₈ may optionally be the radical:##STR10## where y is 0 or 1, R_(a), R_(b) and R_(c) are the same ordifferent and are selected from H-- or alkyl radicals of 1 to 8 carbons,with the proviso that R_(a) and R_(b) may be concatenated to form asubstituted or unsubstituted alkylene diradical of 4 to 11 carbons, withsubstituents being one or more alkyl radicals of 1 to 5 carbons orphenyl radicals;

R₁₉ is selected from the group consisting of alkyl radicals of 1 to 4carbons and, additionally, the two R₁₉ radicals may optionally beconcatenated to form an alkylene diradical of 4 to 5 carbons;

R₁₁ is selected from the group consisting of unsubstituted alkylenediradicals of 2 to 3 carbons, alkylene diradicals of 2 to 3 carbonssubstituted with one or more alkyl radicals of 1 to 4 carbons, anunsubstituted 1,2-phenylene diradical, and 1,2-phenylene diradicalssubstituted with one or more lower alkyl radicals of 1 to 4 carbons,chloro, bromo, nitro or carboxy; and,

X is a direct bond or is selected from the group consisting ofconnecting diradical structures (13), (14), (15) and (16): ##STR11##where (R--Q) shows the point of attachment of the R--Q group to theunsymmetrical X connecting diradical;

z is 1 to 10;

R₂₂ is an alkylene diradical of 2 to 4 carbons, optionally substitutedwith one or more alkyl radicals of 1 to 4 carbons; and,

when the X connecting diradical is Structure (16), R₁ may additionallybe the peroxide containing radical of structure (17): ##STR12##

The tangible embodiments of the first composition aspect of theinvention possess infrared spectrographic, gas and liquidchromatographic and differential scanning calorimetric propertiespositively confirming the structures sought to be patented.

The invention provides in a second composition aspect, novel polymericperoxides derived from the novel polymerizable ethylenically unsaturatedperoxides of the first composition aspect of the invention of structureA, such polymeric peroxides possessing recurring units selected fromstructures B, C, or D: ##STR13## where R, R₁, R₂, R₃ and X have thedefinitions provided hereinabove in the description of the firstcomposition aspect of the invention.

The tangible embodiments of the second composition aspect of theinvention possess infrared spectrographic, gel permeationchromatographic, liquid chromatographic, extractive as well asdifferential scanning calorimetric properties which positively confirmthe structures sought to be patented.

The invention provides in a first process aspect, a process for the useof peroxides of the first composition aspect of the invention as freeradical initiators in amounts effective for the initiation of freeradical reactions selected from among the group of free radicalreactions consisting of:

a) curing unsaturated polyester resin substrates,

b) polymerizing ethylenically unsaturated monomer substrates,

c) crosslinking olefin polymer substrates,

d) curing of elastomer substrates,

e) modifying polyolefin substrates,

f) grafting ethylenically unsaturated monomer substrates onto olefinhomo- and copolymer substrates, and

g) compatibilizing blends of two or more normally incompatible polymersubstrates; which comprises heating said substrates in the presence ofan amount effective for initiating the reaction to be performed of oneor more peroxides of the first composition aspect of the invention for atime sufficient to at least partially decompose said peroxides of thefirst composition aspect of the invention.

The invention provides in a second process aspect, the use of peroxidesof the first composition aspect of the invention in forming the peroxypolymers of the second composition aspect of the invention whichcomprises heating one or more peroxides of the first composition aspectof the invention, in the presence or absence of one or more other freeradical polymerizable ethylenically unsaturated monomers, in thepresence of an amount effective for initiating free radical reactions ofa lower temperature conventional free radical initiator for a timesufficient to at least partially decompose said lower temperatureconventional initiator.

The invention provides in a third process aspect, a process for the useof peroxy polymers of the second composition aspect of the invention incompatibilizing two or more otherwise incompatible polymers whichcomprises;

a) decomposing at least one peroxy polymer of the second compositionaspect of the invention in the presence of a substrate selected from thegroup consisting of free radical poloymerizable monomers and freeradical curable polymers to form a copolymer,

b) incorporating a compatibilizing effective amount of the copolymerformed in step a above into a mixture of two or more otherwiseincompatible polymers each member of which polymer mixture is compatiblewith at least one of the polymeric portions of said copolymer formed instep a.

The invention provides in a fourth process aspect, a process for the useof peroxides of the first composition aspect of the invention incompatibilizing two or more otherwise incompatible polymers whichcomprises decomposing a compatibilizing effective amount of a peroxideof the first composition aspect of the invention in the presence of amixture of two or more normally incompatible polymers.

The invention provides in a third composition aspect, the productsproduced by the process of the first process aspect of the invention.

The invention provides in a fourth composition aspect, as articles ofmanufacture, the products produced by the third process aspect of theinvention.

The invention provides in a fifth composition aspect, as articles ofmanufacture, the products produced by the fourth process aspect of theinvention.

DETAILED DESCRIPTION

The preferred manner of using and making the embodiments of theinvention is detailed specifically as follows:

Utility of the Novel Unsaturated Peroxides of The First CompositionAspect of the Invention

A. Polymerization of Ethylenically Unsaturated Monomers

In the free-radical polymerizations of ethylenically unsaturatedmonomers at suitable temperatures and pressures, the novel unsaturatedperoxides of Structure A of this invention were found to be effectiveinitiators with respect to efficiency (reduced initiator requirements,etc.). Ethylenically unsaturated monomers include olefins, such asethylene, propylene, styrene, alpha-methylstyrene, p-methylstyrene,chlorostyrenes, bromostyrenes, vinylbenzyl chloride, vinylpyridine anddivinylbenzene; diolefins, such as 1,3-butadiene, isoprene andchloroprene; vinyl esters, such as vinyl acetate, vinyl propionate,vinyl laurate, vinyl benzoate and divinyl carbonate; unsaturatednitriles, such as acrylonitrile and methacrylonitrile; acrylic acid andmethacrylic acid and their anhydrides, esters and amides, such asacrylic acid anhydride, allyl, methyl, ethyl, n-butyl, 2-hydroxyethyl,glycidyl, lauryl and 2-ethylhexyl acrylates and methacrylates, andacrylamide and methacrylamide; maleic anhydride and itaconic anhydride;maleic, itaconic and fumaric acids and their esters; vinyl halo andvinylidene dihalo compounds, such as vinyl chloride, vinyl bromide,vinyl fluoride, vinylidene chloride and vinylidene fluoride; perhaloolefins, such as tetrafluroethylene, hexafluoropropylene andchlorotrifluoroethylene; vinyl ethers, such as methyl vinyl ether, ethylvinyl ether and n-butyl vinyl ether; allyl esters, such as allylacetate, allyl benzoate, allyl ethyl carbonate, triallyl phosphate,diallyl phthalate, diallyl fumarate, diallyl glutarate, diallyl adipate,diallyl carbonate diethylene glycol bis(allyl carbonate) (i.e., ADC);acrolein; methyl vinyl ketone; and mixtures thereof.

Temperatures of 0° C. to 250° C., preferably 30° C. to 200° C., arenormally employed in conventional polymerizations and copolymerizationsof ethylenically unsaturated monomers.

Amounts effective for the initiation of free radicals in polymerizationand copolymerization reactions of ethylenically unsaturated monomers arelevels of concentration by weight based on monomers of the unsaturatedperoxide compositions of the first composition aspect of the invention(on a pure basis) of from 0.002% to 3%, preferably from 0.005% to 1%,and more preferably from 0.01% to 0.75%.

The unsaturated peroxides of this invention can be used in combinationwith other free-radical initiators such as those disclosed at the bottomof column 4 and the top of column 5 of U.S. Pat. No. 4,525,308 asnon-invention free-radical initiators. Using the unsaturated peroxidesin combination with these initiators adds flexibility to the processesof polymer producers and allows them to "fine tune" their polymerizationprocesses. Mixtures of two or more unsaturated peroxides can also beused where appropriate.

B. Curing of Unsaturated Polyester Resins

In the curing of unsaturated resin compositions by heating at suitablecuring temperatures in the presence of free-radical curing agents, theunsaturated peroxides of Structure A of this invention exhibit enhancedcuring activity in the curable unsaturated polyester resin compositions.Unsaturated polyester resins that can be cured by the unsaturatedperoxides of this invention usually include an unsaturated polyester andone or more ethylenically unsaturated monomers.

The unsaturated polyesters are, for instance, polyesters as they areobtained by esterifying at least one ethylenically unsaturated di- orpolycarboxylic acid, anhydride or acid halide, such as maleic acid,fumaric acid, glutaconic acid, itaconic acid, mesaconic acid, citraconicacid, allylmalonic acid, tetrahydrophthalic acid, and others, withsaturated and unsaturated di- or polyols, such as ethylene glycol,diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediols, 1,2-,1,3- and 1,4-butanediols, 2,2-dimethyl-1,3-propanediol,2-hydroxymethyl-2-methyl-1,3-propanediol, 2-buten-1,4-diol,2-butyn-1,4-diol, 2,4,4-trimethyl-1,3-pentanediol, glycerol,pentaerythritol, mannitol and others. Mixtures of such di- or polyacidsand/or mixtures of such di- or polyols may also be used. The di- orpolycarboxylic acids may be partially replaced by saturated di- orpolycarboxylic acids, such as adipic acid, succinic acid, sebacic acidand other, and/or by aromatic di- or polycarboxylic acids, such asphthalic acid, trimellitic acid, pyromellitic acid, isophthalic acid andterephthalic acid. The acids used may be substituted by groups such ashalogen. Examples of such suitable halogenated acids are, for instance,tetrachlorophthalic acid, tetrabromophthalic acid,5,6-dicarboxy-1,2,3,4,7,7-hexachlorobicyclo(2.2.1)-2-heptene and others.

The other component of the unsaturated polyester resin composition, thepolymerizable monomer or monomers, can preferably be ethylenicallyunsaturated monomers, such as styrene, alpha-methylstyrene,p-methylstyrene, chlorostyrenes, bromostyrenes, vinylbenzyl chloride,divinylbenzene, diallyl maleate, dibutyl fumarate, triallyl phosphate,triallyl cyanurate, diallyl phthalate, diallyl fumarate, methylacrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate,ethyl acrylate, and others which are copolymerizable with saidunsaturated polyesters. Mixtures of the ethylenically unsaturatedmonomers may also be employed.

A preferred unsaturated polyester resin composition contains as theunsaturated polyester component the esterification product of1,2-propanediol (a polyol), maleic anhydride (an anhydride of anunsaturated polycarboxylic acid) and phthalic anhydride (an anhydride ofan aromatic dicarboxylic acid) as well as the monomer component,styrene.

Other types of unsaturated polyester resin compositions can be curedusing the unsaturated peroxides of this invention as curing catalysts.These resins, called unsaturated vinyl ester resins, consist of a vinylester resin portion and one or more polymerizable monomer components.The vinyl ester resin component can be made by reacting a chloroepoxide,such as epichlorohydrin, with appropriate amounts of a bisphenol such asBisphenol A [2,2-(4-hydroxyphenyl)propane], in the presence of a base,such as sodium hydroxide, to yield a condensation product havingterminal epoxy groups derived from the chloroepoxide. Subsequentreaction of the condensation products with polymerizable unsaturatedcarboxylic acids, such as acrylic acid and methacrylic acid, in thepresence or absence of acidic or basic catalysts, results in formationof the vinyl ester resin component. Normally, styrene is added as thepolymerizable monomer component to complete the preparation of theunsaturated vinyl ester resin composition.

Temperatures of about 20° C. to 200° C. are normally employed.

Amounts effective for the initiation of free radicals in curing ofunsaturated polyester resins are levels of concentration by weight basedon resin of the unsaturated peroxide compositions of the firstcomposition aspect of the invention (on a pure basis) of about 0.05% to5% or more, preferably 0.10% to 4%, more preferably 0.20% to 3%.

The unsaturated polyester resin compositions described above can befilled with various materials, such as sulfur, glass, carbon and boronfibers, carbon blacks, silicas, metal silicates, clays, metalcarbonates, antioxidants (AO's), heat, ultraviolet (UV) and lightstabilizers, sensitizers, dyes, pigments, accelerators, metal oxides,such as zinc oxide, blowing agents, nucleating agents and others.

C. Curing of Elastomers and Crosslinking of Thermoplastic Polymers

In the curing of elastomeric compositions, and the crosslinking ofpolymer compositions, by heating at suitable curing and crosslinkingtemperatures in the presence of free-radical curing and crosslinkingagents, the unsaturated peroxides of Structure A of this inventionexhibit curing and crosslinking activities.

Elastomeric resin compositions that can be cured by the unsaturatedperoxides of this invention include elastomers such asethylene-propylene copolymers (EPR), ethylene-propylene-dieneterpolymers (EPDM), polybutadiene (PBD), silicone rubber (SR), nitrilerubber (NR), neoprene, fluoroelastomers and ethylene-vinyl acetatecopolymer (EVA).

Polymer compositions that can be crosslinked by the unsaturatedperoxides of this invention include olefin thermoplastics such aschlorinated polyethylene (CPE), low density polyethylene (LDPE),linear-low density polyethylene (LLDPE), and high density polyethylene(HDPE). Other crosslinkable thermoplastic polymers includepoly(vinylchloride) (PVC), polystyrene, poly(vinyl acetate),polyacrylics, polyesters, polycarbonate, etc.

Temperatures of about 80° C. to 310° C. are normally employed.

Amounts effective for the initiation of free radicals in curing ofelastomers and crosslinking of thermoplastic polymers are levels ofconcentration by weight based on uncured or uncrosslinked resin of theunsaturated peroxide compositions of the first composition aspect of theinvention (on a pure basis) of from 0.1 to 10%, preferably 0.5% to 5%,more preferably 0.5 to 3%.

The curable elastomeric resin composition or crosslinkable polymercomposition can be optionally filled with the materials listed above foruse with the conventional unsaturated polyester resin compositions.

D. Modification of Polyolefins and Other Polymers

In the processes for modifying polyolefins [e.g., beneficial degradationof polypropylene (PP) by reducing the polymer molecular weight andreducing the polymer molecular weight distribution and enhancing themolecular weight and film forming properties of linear low densitypolyethylene (LLDPE)] and copolymers, the unsaturated peroxides ofStructure A of this invention exhibit polyolefin modification activity.Other polymers that can be modified with unsaturated peroxides includeHDPE, ethylene-propylene copolymer, etc.

Temperatures of about 140° C. to 340° C. are normally employed.

Amounts effective for the initiation of free radicals in themodification of polyolefins and other polymers are levels ofconcentration by weight based on unmodified polyolefin or otherunmodified polymer of unsaturated peroxide compositions of the firstcomposition aspect of the invention (on a pure basis) of about 0.001% to1.0%, preferably 0.01% to 1%, more preferably 0.01% to 0.5%.

Optionally, up to 1% by weight of molecular oxygen can be employed as amodification co-catalyst.

Utility of Polymeric Peroxide Derivatives of the Second CompositionAspect of the Invention

The novel polymeric peroxides of the second composition aspect of theinvention have utility in several applications. They can be used toprepare block and graft copolymers by several techniques. A graftcopolymer of the polymeric peroxide derivative can be made by using thepolymeric peroxide derivative as the backbone polymer as well as theinitiator, and grafting monomers onto this backbone. A graft copolymercontaining two or more monomers that are not the same as the monomer(s)of Structure A in a particular polymeric peroxide of the secondcomposition aspect of the invention can be made by partially decomposingthe polymeric peroxide first in the presence of one monomer followed bydecomposing in the presence of a second monomer, etc. The graftingprocesses can be carried out in solution or in polymer processingequipment such as extruders. Such graft copolymers have utility incompatibilizing homopolymer and copolymer blends and alloys.

The polymeric peroxides of the second composition aspect of theinvention can also be used in reactive processing to compatibilizepolymers in situ by forming block and graft copolymers in polymerprocessing equipment such as extruders, roll mills, etc.

The polymeric peroxides of the second composition aspect of theinvention can also be used to enhance the quality of interpenetratingpolymer networks (IPN's) in polymer processing equipment.

Polymeric peroxides of the second composition aspect of the inventioncan be used in reactive processing to enhance the impact resistance ofpolymer blends.

The polymeric peroxides of the second composition aspect of theinvention also have utility as polymeric low profile/low shrink curingagents, as self-curing polymeric systems and as self degrading polymersystems.

Finally, the polymeric peroxides of the second composition aspect of theinvention are the ultimate in polymer-peroxide master batches (i.e.,polymer-peroxide composition with up to 5% or more of organic peroxides,useful in crosslinking, curing and polymer modification applications)since the peroxide functions are compatible with the polymer backbone(covalently attached) and cannot bloom, exude or volatilize.

Preparations of the Novel Unsaturated Peroxides of Structure A

Several synthetic methods can be used for preparations of the novelunsaturated peroxides of Structure A. One method is to react a hydroxysubstituted peroxide with an unsaturated acid halide, an unsaturatedhaloformate or an unsaturated cyclic acid anhydride in the presence of asuitable base and an optional solvent. Suitable bases includetriethylamine, tributylamine, N,N-dimethylaniline, urea,tetramethylurea, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, calcium hydroxide, barium hydroxide, calcium carbonate andtrisodium phosphate. Reaction of hydroxy substituted peroxides withunsaturated cyclic anhydrides can take place in the presence of a strongorganic or strong inorganic acid. Suitable strong organic or stronginorganic acids include methanesulfonic acid, benzenesulfonic acid,toluenesulfonic acid, sulfuric acid, sodium hydrogen sulfate, potassiumhydrogen sulfate, perchloric acid, nitric acid, hydrochloric acid,phosphoric acid, and mixtures thereof.

Another synthetic route to the unsaturated peroxides of Structure Ainvolves reaction of a hydroxy substituted peroxide with an unsaturatedisocyanate with or without an optional solvent and preferably in thepresence of a suitable catalyst, such as an alkyltin salt, for instance,dibutyltin dilaurate.

Another synthetic route to the unsaturated peroxides of Structure Ainvolves reaction of an unsaturated ketone with a t-alkyl hydroperoxidein the presence of a strong organic or inorganic acid.

Yet another synthetic route to certain unsaturated peroxides ofStructure A involves reaction of certain unsaturated hydroxy compoundsof the structures: ##STR14## with certain peroxides with haloformategroups, in the presence of suitable bases and optional solvents, to formunsaturated peroxides of the structures: ##STR15## respectively.

A specific synthetic route to certain unsaturated peroxides of StructureA involves reaction of an unsaturated haloformate of the structure:##STR16## with a t-alkyl hydroperoxide in the presence of suitable basesand optional solvents, to form an unsaturated peroxide of the structure:##STR17## Hydroxy substituted peroxides that may be used for thepreparations of the novel unsaturated peroxides of Structure A, can beprepared by methods well known in the art (U.S. Pat. Nos. 3,236,872,4,525,308, and European Patent Application 0381135 A2). Non-limitingexamples of hydroxy substituted peroxides include,2-(t-butylperoxy)-2-methyl-4-hydroxypentane,2-(t-amylperoxy)-2-methyl-4-hydroxypentane,2-(t-butylperoxy)-2-methyl-4-hydroxybutane,2-(t-amylperoxy)-2-methyl-4-hydroxybutane, OO-t-butyl O-(2-hydroxyethyl)monoperoxysuccinate, OO-t-butyl O-(2-hydroxyethyl) monoperoxyphthalate,3-hydroxy-1,1-dimethylbutyl peroxy-2-methylbenzoate,2-methoxy-2-(3-hydroxy-1,1-dimethylbutylperoxy)propane3-hydroxy-1,1-dimethylbutyl peroxy-2-ethylhexanoate,3-hydroxy-1,1-dimethylbutyl peroxyacetate, 3-hydroxy-1,1-dimethylbutylperoxyisobutyrate, 3-hydroxy-1,1-dimethylbutyl peroxyneoheptanoate, and,di-(3-hydroxy-1,1-dimethylbutyl)peroxide.

Non-limiting examples of peroxides possessing haloformate groups, whichare reactive with certain unsaturated alcohols, include,1,3-dimethyl-3-(t-butylperoxy)butyl chloroformate,3-methyl-3-(t-butylperoxy)butyl chloroformate,1,3-dimethyl-3-(t-amylperoxy)butyl chloroformate,3-methyl-3-(t-amylperoxy)butyl chloroformate,1,3-dimethyl-3-(2-ethylhexanoylperoxy)butyl chloroformate,1,3-dimethyl-3-(neoheptanoylperoxy)butyl chloroformate,1,3-dimethyl-3-(neodecanoylperoxy)butyl chloroformate,3,3-di-(t-butylperoxy)butyl chloroformate,1,3-dimethyl-3-(2-methylbenzoylperoxy)butyl chloroformate anddi-(1,3-dimethyl-3-chlorocarbonyloxybutyl) peroxide.

These haloformate containing peroxides can be prepared by reacting thecorresponding hydroxy substituted peroxides with excess carbonyldihalide (e.g., phosgene) under conditions effective for formation ofthe haloformate.

Non-limiting examples of t-alkyl hydroperoxides which can be used in thesynthetic processes for preparing certain unsaturated peroxides ofStructure A, include, t-butyl hydroperoxide, t-amyl hydroperoxide,t-hexyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumenehydroperoxide, 3-hydroxy-1,1-dimethylbutyl hydroperoxide,1-methylcyclohexyl hydroperoxide and 3-methyl-3-hydroperoxy-1-butyne.

Non-limiting examples of certain unsaturated hydroxy compounds that arereactive with peroxides containing haloformate groups, include,2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethoxyethylacrylate and TONE™ 100. (TONE 100 is a hydroxy acrylate monomer of thestructure: ##STR18## which is manufactured by the Union CarbideCorporation.)

Non-limiting examples of unsaturated acid halides, haloformates andcyclic anhydrides that can be reacted with hydroxy substituted peroxidesto form the novel unsaturated peroxides of Structure A, include,acryloyl chloride, methacryloyl chloride, 2-acryloxyethyl chloroformate,2-methacryloxyethyl chloroformate, 2 -acryloxypropyl chloroformate,fumaryl chloride, alkyl fumaryl chlorides (such as ethyl fumarylchloride) maleic anhydride, itaconic acid anhydride and TONE 100chloroformate.

Non-limiting examples of unsaturated isocyanates that can be reactedwith hydroxy substituted peroxides to form the novel unsaturatedperoxides of Structure A, include, isocyanatoethyl methacrylate,1-(1-isocyanato-1-methylethyl)-3-(1 methylethenyl)benzene, and1-(1-isocyanato-1-methylethyl)-4-(1-methylethenyl)benzene.

Non-limiting examples of unsaturated ketones that can be reacted withhydroperoxides and strong organic and inorganic acids to form certainnovel unsaturated diperoxyketals of Structure A, include,2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl methacrylate.

Non-limiting examples of optional solvents useful for and in thepreparation of the novel unsaturated peroxides (Structure A) of thisinvention include pentane, hexanes, heptanes, dodecanes, odorlessmineral spirits mixtures, toluene, xylenes, cumene, methylene chloride,ethyl acetate, 2-ethylhexyl acetate, isobutyl isobutyrate, dimethyladipate, dimethyl succinate, dimethyl glutarate (or mixtures thereof),dimethyl phthalate, dibutyl phthalate, benzyl butyl phthalate, diethylether, methyl t-butyl ether, 2-methoxyethyl acetate and others.

Non-limiting examples of the novel unsaturated peroxides of Structure A,in addition to those in the examples, include the following:

ethyl 1,3-dimethyl-3-(t-amylperoxy)butyl fumarate,

di-[1,3-dimethyl-3-(t-amylperoxy)butyl] fumarate,

1,3-dimethyl-3-(t-amylperoxy)butyl hydrogen maleate,

3-methyl-3-(t-butylperoxy)butyl methacrylate,

3-methyl-3-(t-butylperoxy)butyl acrylate,

1,3-dimethyl-3-(t-amylperoxy)butyl methacrylate,

1,3-dimethyl-3-(t-amylperoxy)butyl acrylate,

3-methyl-3-(t-amylperoxy)butyl methacrylate,

3-methyl-3-(t-amylperoxy)butyl acrylate,

1,3-dimethyl-3-(2-ethylhexanoylperoxy)butyl methacrylate,

1,3-dimethyl-3-(2-ethylhexanoylperoxy)butyl acrylate,

1,3-dimethyl-3-(neoheptanoylperoxy)butyl methacrylate,

1,3-dimethyl-3-(neodecanoylperoxy)butyl acrylate,

1,3-dimethyl-3-(2-methylbenzoylperoxy)butyl methacrylate,

1,3-dimethyl-3-(2-methylbenzoylperoxy)butyl acrylate, and

di-(3-acryloyloxy-1,1-dimethylbutyl) peroxide.

Preparations of the Novel Polymeric-Peroxides of The Second CompositionAspect of The Invention

Novel polymeric-peroxides derived from the novel polymerizable,unsaturated peroxide compositions of Structure A, can be prepared suchthat the polymeric-peroxides produced possess recurring units selectedfrom Structures B, C and D as set forth herein above.

In general, the novel unsaturated peroxides of the instant invention canbe homopolymerized under self-initiating conditions or withnon-invention free-radical initiators under conditions effective forinitiating polymerization of the novel unsaturated peroxides ofStructure A, thus producing novel polymeric peroxides possessing pendantperoxide groups. The novel unsaturated peroxides of the instantinvention can also be copolymerized with co-monomers under similarconditions to produce novel copolymeric peroxides possessing pendantperoxide groups.

Non-limiting examples of co-monomers that may be copolymerized with thenovel unsaturated peroxides of this invention to produce novel polymericperoxides, include, ethylene, propylene, butadiene, isoprene,chloroprene, vinyl chloride, acrylonitrile, styrene,alpha-methylstyrene, p-methylstyrene, methyl acrylate, ethyl acrylate,butyl acrylate, butyl methacrylate, 2-hydroxyethyl methacrylate,2-ethylhexyl methacrylate, methyl methacrylate, acrylamide, acrylicacid, methacrylic acid, maleic anhydride, ethyl vinyl ether, vinylacetate, acrolein, glycidyl vinyl ether, and mixtures thereof.

Non-limiting, non-invention free-radical initiators useful forinitiating homo- and copolymerizations of the novel unsaturatedperoxides of Structure A include; peroxyesters such as, t-butylperoxyacetate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butylperoxybenzoate, t-butyl peroxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butylperoxyneoheptanoate, t-butyl peroxyneodecanoate, t-amyl peroxyacetate,t-amyl peroxy-3,5,5-trimethylhexanoate, t-amyl peroxybenzoate, t-amylperoxyisobutyrate, t-amyl peroxy-2-ethylhexanoate, t-amylperoxypivalate, t-amyl peroxyneoheptanoate, t-amyl peroxyneodecanoate,1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate,1,1,3,3-tetramethylbutyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxyneoheptanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate,3-hydroxy-1,1-dimethylbutyl peroxy-2-ethylhexanoate,3-hydroxy-1,1-dimethylbutyl peroxyneoheptanoate,3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate,2,5-dimethyl-2,5-di(benzoylperoxy)hexane,2,5-dimethyl-2,5-di-(2-ethylhexanoylperoxy)hexane, alpha-cumylperoxyneoheptanoate and alpha-cumyl peroxyneodecanoate; diacyl peroxidessuch as dibenzoyl peroxide, didecanoyl peroxide, didodecanoyl peroxideand di-(3,5,5-trimethylhexanoyl) peroxide; peroxydicarbonates such asdipropyl peroxydicarbonate, di-(2-butyl) peroxydicarbonate, diisopropylperoxydicarbonate, dicyclohexyl peroxydicarbonate,di-(4-t-butylcyclohexyl) peroxydicarbonate and di-(2-ethylhexyl)peroxydicarbonate; diperoxyketals such as 2,2-di-(t-butylperoxy)butane,2,2-di-(t-butylperoxy) propane, 1,1-di-(t-butylperoxy)cyclohexane,1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane, ethyl3,3-di-(t-butylperoxy)butyrate, n-butyl4,4-di-(t-butylperoxy)pentanoate, 2,2-di-(t-amylperoxy)butane,2,2-di-(t-amylperoxy)propane, 1,1-di-(t-amylperoxy)cyclohexane,1,1-di-(t-amylperoxy)-3,3,5-trimethylcyclohexane, ethyl3,3-di-(t-amylperoxy)butyrate and n-butyl4,4-di-(t-amylperoxy)pentanoate; OO-t-alkyl O-alkyl monoperoxycarbonatessuch as OO-t-butyl O-isopropyl monoperoxycarbonate, OO-t-butylO-(2-ethylhexyl) monoperoxycarbonate, OO-t-amyl O-isopropylmonoperoxycarbonate and OO-t-amyl O-(2-ethylhexyl) monoperoxycarbonate;dialkyl peroxides such as di-t-butyl peroxide, t-butyl alpha-cumylperoxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane,2,5-dimethyl-2,5-di-(t-butylperoxy)-3-hexyne, di-t-amyl peroxide, t-amylalpha-cumyl peroxide and 2,5-dimethyl-2,5-di-(t-amylperoxy)hexane; andazo initiators such as azobis(isobutyronitrile).

The polymerization conditions used to homo- and copolymerize the novelunsaturated peroxides of Structure A will vary with the type of monomerused, but generally the conditions for a specific monomer will besimilar to those known in the art. The only requirement is that thereaction temperatures, times, solvents, initiators, and catalysts aresuch that substantial degradation of the novel unsaturated peroxide orof the resulting polymeric peroxy containing recurring units does notoccur.

Temperatures of about 0° C. to 250° C., preferably 20° C. to 200° C.,and non-invention initiator levels of 0.002% to 3%, preferably 0.003% to1% by weight based on polymerizable monomers, are normally employed forthe homo- and copolymerizations of the novel unsaturated peroxides ofStructure A to produce the novel polymeric peroxides of the secondcomposition aspect of the invention.

The polymeric peroxides of the second composition aspect of theinvention can also be prepared by initially homo- or copolymerizing anethylenically unsaturated monomer which possesses a functional groupthat is reactive with hydroxy peroxides. The conditions for the homo- orcopolymerization reactions are similar to those given above.Non-limiting examples of reactive monomers include acryloyl chloride,methacryloyl chloride, isocyanatoethyl methacrylate,1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene and1-(1-isocyanato-1-methylethyl)-4-(1-methylethenyl)benzene. The initiallyformed homo- or copolymers possess pendant reactive groups whichsubsequently are reacted with hydroxy peroxides to produce the novelpolymeric peroxides of the second composition aspect of the invention.Examples of reactive hydroxy peroxides are given above. It should benoted that Example 16 illustrates this method.

Preparative Examples

The following examples further illustrate the best mode contemplated bythe inventors for the practice of their invention, are presented toprovide detailed preparative illustrations and are not intended to limitthe scope of the present invention.

EXAMPLE 1 Preparation of 1,3-Dimethyl-3-(t-butylperoxy)butylN-(1-{3-(1-Methylethenyl)phenyl}-1-methylethyl]carbamate (PM-1)

Reaction of 1,3-dimethyl-3-(t-butylperoxy)butanol with1(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene:

An Erlenmeyer flask was charged with 10 g of toluene, 12.0 g (57.0mmoles) of 90.4% 1,3-dimethyl-3-(t-butylperoxy)butanol, 10.6 g (52.7mmoles of 1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene[TMI, manufactured by the American Cyanamid Company], and 0.1 g ofdibutyltin dilaurate (catalyst). The flask was fitted with a refluxcondenser and was placed in a 70° C. water bath, and the reactionmixture was stirred magnetically for 2 hours. The reaction mixture wasthen allowed to stand overnight (ca. 15 hours) at room temperature. Thereaction mixture was then reheated to 60° C. to dissolve the precipitatethat formed. Next, 10 mL of methanol was added and the reaction mixturewas stirred for 0.5 hour. As much of the solvent as was possible wasremoved using a rotary evaporator. The resultant slurry was dissolved inhot hexane to form a clear solution. Upon cooling to -20° C. a whiteprecipitate formed, which was suction filtered and dried to yield 18.1 g(87.9%) of a white powder, mp 68°-70° C. Analysis of the product byinfrared spectroscopy (KBr) showed a strong carbonyl absorption at 1680cm⁻¹ and the absence of an iscoyanate absorption at 2260 cm⁻¹. Analysisof the product by gas chromatography indicated that it contained lessthan 0.1% residual starting peroxide. A rapid heat, test showed aperoxide decomposition at about 147° C.

EXAMPLE 2 Preparation of 3-Methyl-3-(t-butylperoxy)butylN-[1-{3-(1-Methylethenyl)phenyl}-1-methylethyl]carbamate (PM-2)

Reaction of 3-methyl-3-(t-butylperoxy butanol with1-(1-isocyanatio-1-methylethyl)-3-(1-methylethenyl)benzene:

A process similar to that employed in Example 1 was used to prepare thetitle peroxy monomer (PM-2) via reaction of3-methyl-3-(t-butylperoxy)butanol with TMI. A liquid product wasobtained in a crude yield of 85%. Analysis of the product by infraredspectroscopy showed an NH band at about 3320 cm⁻¹, broad carbonylabsorption bands at 1720 cm⁻¹ and at 1690 cm⁻¹ and the absence of anisocyanate absorption band at 2260 cm⁻¹. Analysis by high performanceliquid chromatography indicated that 4.5% residual starting peroxide[3-methyl-3-(t-butylperoxy)butanol] remained in the product. Analysis ofthe product by differential scanning calorimetry (DSC) showed a majorperoxide decomposition exotherm at about 187° C.

The results of the above analyses and the method of preparationdemonstrate that the desired titled peroxy monomer (PM-2) was thepredominant component of the product produced in this example.

EXAMPLE 3 Preparation ofDi-[1,1-dimethyl-3-(1-{3-(1-methylethenyl)}phenyl-1-methylethylaminocarbonyloxy)butyl]Peroxide (PM-3)

Reaction of di-(3-hydroxy-1,1-dimethylbutyl) peroxide with1-(1-isocyanato-1-methylethyl)-3-(1-methylethyl)benzene:

A process similar to that employed in Example 1 was used to prepare thetitle peroxy monomer (PM-3) via reaction of one mole ofdi-(3-hydroxy-1,1-dimethylbutyl) peroxide with two moles of TMI. A whitesolid product was obtained in a crude yield of 61%. The melting pointwas found to be 111°-114° C. Analysis of the product by infraredspectroscopy showed an NH band at about 3330 cm⁻¹, a carbonyl absorptionband at 1680 cm⁻¹ and the absence of an isocyanate absorption band at2260 cm⁻¹. Analysis by high performance liquid chromatography indicatedthat the purity of the product was about 92%. Analysis of the product bydifferential scanning calorimetry (DSC) showed a major peroxidedecomposition exotherm at about 189° C.

The analysis results and the method of preparation demonstrated that thedesired title peroxy monomer (PM-3) was the predominant component of theproduct produced in this example.

EXAMPLE 4 Preparation of 1,3-Dimethyl-3-(2-methylbenzoylperoxy)butylN-(1-{3-Methylethenyl)phenyl}-1-methylethyl]carbamate (PM-4)

Reaction of 3-hydroxy-1,1-dimethylbutyl peroxy-2-methylbenzoate with1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene:

A 3-necked flask fitted with a thermometer and a reflux condenser wascharged with 10.0 g (39.6 mmoles) of 3-hydroxy-1,1-dimethylbutylperoxy-2-methylbenzoate, 8.0 g (39.7 mmoles) of TMI, 60 g of toluene,and 0.1 g of dibutyltin dilaurate. The reaction mixture was heated to60° C. for 2 hours, whereupon another 0.1 g of dibutyltin dilaurate wasadded. After an additional 2 hours at 60° C., a sample of the reactionmixture was analyzed by infrared spectroscopy which showed that only asmall isocyanate band remained. Then 10 mL of methanol was added, andthe reaction mixture was stirred for 0.5 hour. Removal of the solventusing a rotary evaporator and a vacuum pump afforded 18.0 g (100%) of aviscous yellow oil. Analysis of the oil by infrared spectroscopy showeda large carbonyl band at 1725 cm⁻¹ and the absence of an isocyanate bandall 2260 cm⁻¹. Analysis by high performance liquid chromatographyindicated that 8.6% residual starting peroxide remained.

The above results demonstrate that most of the starting peroxide reactedwith the isocyanate to form the desired product.

EXAMPLE 5 Preparation of 1,3-Dimethyl-3-(t-amylperoxy)butylN-[1-{3-(1-Methylethenyl)phenyl}-1-methylethyl]carbamate (PM-5)

Reaction of 1,3-dimethyl-3-(t-amylperoxy) butanol with1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene:

A 3-necked flask which was fitted with a thermometer and a refluxcondenser was charged with 50.0 g (234.9 mmoles) of 96%1,3-dimethyl-3-(t-amylperoxy)butanol, 47.3 g (235.0 mmoles) of TMI, 60 gof toluene, and 1.0 g of dibutyltin dilaurate. The resultant solutionwas magnetically stirred and was heated in a 70° C. water bath for 2hours. Analysis of a sample of the reaction mixture by infraredspectroscopy indicated that no isocyanate was present. The reactionmixture was diluted with 60 mL of methanol and was stirred for another0.5 hour. As much of the solvent as was possible was removed using arotary evaporator, and the resultant slurry was diluted with hexane,cooled to -20° C., and suction filtered. Obtained was 59.6 g (62.5%) ofa white powder, mp 53°-55° C. An infrared spectrum (KBr) showed a strongcarbonyl band at 1690 cm⁻¹ indicative of a carbamate and the absence ofan isocyanate band at 2260 cm⁻¹.

The above results demonstrate that the desired title peroxide wasformed.

EXAMPLE 6 Preparation of Ethyl 1,3-Dimethyl-3-(t-butyl-peroxy)butylFumarate (PM-6)

Reaction of 1,3-dimethyl-3-(t-butylperoxy)butanol withtrans-3-ethoxycarbonyl-2-propenoyl chloride (ethyl fumaryl chloride) inthe absence and in the presence of common bases such as NaOH, KOH, Na₂CO₃, KHCO₃, K₂ CO₃, triethylamine and other inorganic and organic basesfailed to yield the desired titled product.

Surprisingly, a highly substituted urea, 1,1,3,3-tetramethylurea, wasfound to be an effective base for reaction of ethyl fumaryl chloridewith 1,3-dimethyl-3-(t-butylperoxy)butanol. The synthetic procedureusing 1,1,3,3-tetramethylurea as a base for preparing the titledperoxide (PM-6) is described below.

A 250 mL 3-neck flask equipped with a magnetic stirrer, a thermometer, acondenser and an addition funnel was charged with 100 mL of methylt-butyl ether, 17.4 g (0.15 mole) of 1,1,3,3-tetramethylurea (TMU) and14.7 g (0.07 mole) of 90.7% 1,3-dimethyl-3-(t-butylperoxy)butanol. Tothe resulting stirred solution at 21°-27° C. was slowly added 11.4 g(0.07 mole) of 100% trans-3-ethoxycarbonyl-2-propenoyl chloride (ethylfumaryl chloride) over a period of 10 minutes. The resulting solutionwas then stirred for ca. 6 hours at 50° C. The solution was then pouredinto 100 mL of water and the methyl t-butyl ether layer was separated.The methyl t-butyl ether layer was then washed twice with 50 mL portionsof aqueous 10% KOH solution and then with 50 mL portions of water untilthe pH was about 7. After drying over about 10% by weight of anhydrousMgSO₄ the spent desiccant was separated by filtration and the solventwas removed in vacuo leaving 18.6 g (84% of theory, uncorrected) of anamber liquid product. An infrared spectrum of the product showed astrong ester carbonyl band at ca. 1720 cm⁻¹ and a carbon-carbon doublebond band at ca. 1640 cm⁻¹. A liquid chromatography scan showed a majorpeak which indicated ca. 92.5% product purity according to area percent.According to gas chromatography the product also contained ca. 5% of1,3-dimethyl-3-(t-butylperoxy)butanol, one of the reactants. Based onliquid chromatographic purity the corrected yield for the product wasca. 78%.

Based on the method of preparation, yield data, infrared data and liquidchromatographic data the product obtained in this reaction was thedesired titled prduct, ethyl 1,3-dimethyl-3-(t-butylperoxy)butylfumarate (PM-6).

EXAMPLE 7 Preparation of Di-[1,3-Dimethyl-3-(t-butylperoxy)butyl]Fumarate (PM-7)

Reaction of 1,3-dimethyl-3-(t-butylperoxy) butanol with fumaryl chloridein the absence and in the presence of common bases such as NaOH, KOH,NaHCO₃, Na₂ CO₃, KHCO₃, Na₂ CO₃, triethylamine and other inorganic andorganic bases failed to yield the desired titled product.

1,1,3-3-Tetramethylurea, was found to be an effective base for reactionof fumaryl chloride with 1,3-dimethyl-3-(t-butylperoxy) butanol. Thesynthetic procedure using 1,1,3,3-tetramethylurea as a base forpreparing the titled peroxide (PM-7) is described below.

A 250 mL 3-neck flask equipped with a magnetic stirrer, a thermometer, acondenser and an addition funnel was charged with 100 mL of methylt-butyl ether, 28.0 g (0.24 mole) of 1,1,3,3-tetramethylurea (TMU) and14.7 g (0.07 mole) of 90.7% 1,3-dimethyl-3-(t-butylperoxy)butanol. Tothe resulting stirred solution at 20°-25° C. was slowly added 5.6 g(0.035 mole) of 95% fumaryl chloride over a period of 10 minutes. Theresulting solution was stirred for ca. 7.5 hours at 50°-60° C., thencooled to 20° C. and an additional 100 mL of methyl t-butyl ether wasadded to the reaction mass. The solution was then poured into 100 mL ofwater and the methyl t-butyl ether layer was separated. The methylt-butyl ether layer was then washed twice with 50 mL portions of aqueous5% KOH solution, then washed with a 50 mL portion of aqueous 3%hydrochloric acid solution and then with 50 mL portions ,of water untilthe pH was about 7. After drying over about 10% by weight of anhydrousMgSO₄ the spent desiccant was separated by filtration and the solventwas removed in vacuo leaving 13.6 g (84% of theory, uncorrected) of alight yellow liquid product. An infrared spectrum of the product showeda strong ester carbonyl band at ca. 1740 cm⁻¹ and a small carbon-carbondouble bond band at ca. 1645 cm⁻¹. A liquid chromatography scan showed amajor peak which indicated ca. 90% desired product and ca. 10%1,3-dimethyl-3-(t-butylperoxy)butanol, one of the reactants. Based onthe liquid chromatographic purity the corrected yield for the productwas ca. 76%.

Based on the method of preparation, yield data, infrared data and liquidchromatoraphic data the product obtained in this reaction was thedesired titled product, di-[1,3-dimethyl-3-(t-butylperoxy)butyl]fumarate (PM-7).

EXAMPLE 8 Preparation of 1,3-Dimethyl-3-(t-butylperoxy)butyl HydrogenMaleate (PM-8)

A 100 mL 3-neck flask equipped with a magnetic stirrer, a thermometerand a condenser was charged with 21.1 g (0.10 mole) of 90.7%1,3-dimethyl-3-(t-butylperoxy)butanol, 12.5 g (0.125 mole) of maleicanhydride and 6 drops of aqueous 50% sulfuric acid solution. The stirredreaction mixture was then heated to and held at 55°-65° C. for about 6hours after which the reaction mixture was cooled to room temperatureand poured into 100 mL of water. The organic layer that resulted wasextracted with 200 mL of methyl t-butyl ether and the methyl t-butylether solution was washed with 100 mL of water at 30°-35° C. Theresulting solution was dried over about 10% by weight of anhydrousMgSO₄. The spent desiccant was separated by filtration and the solventwas removed in vacuo leaving 12.2 g (42% of theory, uncorrected) of aliquid product. An infrared spectrum of the product showed a small OHband, an anhydride carbonyl band at about 1785 cm⁻¹, a strong estercarbonyl band at ca 1740 cm⁻¹ and a carbon-carbon double bond band atca. 1650 cm⁻¹. The product was then poured into 100 mL of aqueous 3%NaOH solution, stirred for 5 minutes at 20°-25° C. in order to preparethe sodium salt of the title product and to hydrolyze the excess maleicanhydride. The salt solution was extracted twice with 100 mL portions ofpentane in order to remove neutral impurities. The salt solution wasthen brought to a pH of 2-3 with dilute hydrochloric acid solution andthe resulting mixture was extracted twice with 100 mL portions of methylt-butyl ether and the methyl t-butyl ether extracts were combined. Theresulting solution was dried over about 10% by weight of anhydrous MgSO₄the spent desiccant was separated by filtration and the solvent wasremoved in vacuo leaving 11.2 g (39% of theory, uncorrected) of a lightyellow liquid product. A liquid chromatography scan showed a major peakwhich indicated ca. 96% product purity according to area percent. Theliquid chromatography scan of the product also showed that it containeda minor amount of 1,3-dimethyl-3-(t-butylperoxy)butanol, one of thereactants. Based on the liquid chromatographic purity the correctedyield for the product was ca. 37%. Analysis of the product bydifferential scanning calorimetry (DSC) showed a major peroxidedecomposition exotherm at about 170° C.

Based on the method of preparation, yield data, infrared data, liquidchromatographic data and DSC data the product obtained in this reactionwas the desired title product, 1,3-dimethyl-3-(t-butylperoxy)butylhydrogen maleate (PM-8).

EXAMPLE 9 Preparation of 1,3 -Dimethyl-3-(t-butylperoxy)butylMethacrylate (PM-9)

A 300 mL 3-neck flask equipped with a magnetic stirrer, a thermometer, acondenser and an addition funnel was charged with 150 mL of methylt-butyl ether, 19.8 g (0.25 mole) of pyridine and 41.7 g (0.20 mole) of92% 1,3-dimethyl-3-(t-butylperoxy)butanol. To the resulting stirredsolution at 21°-27° C. was slowly added 24.4 g (0.21 mole) of 90%methacryloyl chloride over a period of 45 minutes. The resultingsolution was then stirred for ca. 6 hours at 25°-30° C. after which thereaction mixture was poured into 300 mL of water and the methyl t-butylether layer was separated. The water layer was extracted with one 100 mLportion of methyl t-butyl ether. The combined portions of methyl t-butylether were then washed with a 150 mL portion of aqueous 5% HCl solutionand then twice with 100 mL portions of aqueous 3% NaHCO₃ solution. Afterdrying over about 10% by wieght of anhydrous MgSO₄, the spent desiccantwas separated by filtration and the solvent was removed in vacuo leaving38.2 g (74% of theory, uncorrected) of a light yellow liquid product. Aninfrared spectrum of the product showed no OH band in the OH bandregion, a strong ester carbonyl band at ca. 1720 cm⁻¹ and acarbon-carbon double bond band at ca. 1640 cm⁻¹. According to gaschromatography the product also contained ca. 5% of1,3-dimethyl-3-(t-butylperoxy)butanol, one of the reactants.

Based on the method of preparation, yield data and infrared data theproduct obtained in this reaction was the desired titled product,1,3-dimethyl-3-(butylperoxy)butyl methacrylate (PM-9).

EXAMPLE 10 Preparation of 1,3-Dimethyl-3-(t-butylperoxy)butyl Acrylate(PM-10)

A process similar to that employed in Example 9 was used to prepare thetitle peroxy monomer (PM-10) via reaction of1,3-dimethyl-3-(t-butylperoxy)butanol (0.266 mole) with acryloylchloride (0.346 mole) in the presence of triethylamine (0.359 mole) andN-methylpyrrolidone (ca. 230 mL, reaction solvent). After isolation ofthe crude liquid product in 93% yield, the product was distilled at 48°C./0.1 torr., resulting in a 72.7% yield of colorless liquid. Analysisof the distilled product by infrared spectroscopy showed an estercarbonyl absorption band at 1722 cm⁻¹ and an olefinic band at 1620-1640cm⁻¹. Analysis by high performance liquid chromatography showed only onepeak. This indicated that the distilled product was of very high purity.Analysis of the product by differential scanning calorimetry (DSC)showed a major peroxide decomposition exotherm at about 186° C.

Based on the method of preparation, yield data, liquid chromatographydata, DSC data and infrared data the product obtained in this reactionwas the desired title product, 1,3-dimethyl-3-(t-butylperoxy) butylacrylate (PM-10).

EXAMPLE 11 Preparation of 1,3-Dimethyl-3-(t-butylperoxy)butyl TONE-100Carbonate (PM-11)

In this reaction 1,3-dimethyl-3-(t-butylperoxy)butyl chloroformate wasreacted with TONE-100 in the presence of triethylamine as a base.TONE-100 is a hydroxy acrylate monomer of the structure: ##STR19##manufactured by the Union Carbide Corporation. TONE-100 was initiallydried by dissolving 13.3 g (37.8 mmoles) of TONE-100 in 75 mL of dryethyl acetate, adding ca. 10% by weight of anhydrous MgSO₄, stirring,separating the spent desiccant by filtration and washing the spentdesiccant with 25 mL of dry ethyl acetate. The combined ethyl acetatesolution was added to a 300 mL 3-neck flask equipped with a magneticstirrer, a thermometer, a condenser and an addition funnel. The 300 mL3-neck flask was also charged with 0.1 g of p-N,N-dimethylaminopyridine(DMAP) and 5.7 g (56.3 mmoles) of triethylamine. To the resultingstirred solution at room temperature was slowly added 10.0 g (37.8mmoles) of 96% 1,3-dimethyl-3-(t-butylperoxy)butyl chloroformate over aperiod of 15 minutes. The resulting reaction mixture was then stirred atroom temperature for about 2 hours after which the reaction mixture waswashed several times with aqueous 10% HCl solution and then once with100 mL saturated aqueous NaHCO₃ solution. After drying over about 10% byweight of anhydrous MgSO₄ the spent desiccant was separated byfiltration and the solvent was removed in vacuo leaving 20.8 g (96% oftheory, uncorrected) of a light yellow liquid product. An infraredspectrum of the product, showed a small OH band centered at ca. 3500cm⁻¹, a strong carbonate carbonyl band at ca. 1740 cm⁻¹, a strong estercarbonyl band at ca 1700 cm⁻¹, a weak carbon-carbon double bond band atca. 1640 cm⁻¹ and an --OO-- band at ca. 875 cm⁻¹. According to gaschromatography the product also contained ca. 6%1,3-dimethyl-3-(t-butylperoxy)butanol, a hydrolysis product derived from1,3-dimethyl-3-(t-butylperoxy)butyl chloroformate, one of the reactants.

Based on the method of preparation, yield data and infrared data, theproduct obtained in this reaction was the desired title product,1,3-dimethyl-3-(t-butylperoxy)butyl TONE-100 carbonate (PM-11).

EXAMPLE 12 Preparation of OO-t-Butyl O-(TONE-100) Monoperoxycarbonate(PM-12)

In this reaction t-butyl hydroperoxide was reacted with TONE-100chloroformate in the presence of NaOH (aqueous 10%) as a base. TONE-100chloroformate was initially prepared in an assay of 93% and in acorrected yield of 51% by reacting TONE-100 with excess phosgene.

A 250 mL jacketed reactor equipped with a mechanical stirrer, athermometer and an addition funnel was charged with 44.0 g (0.11 mole)of aqueous 10% NaOH solution and 10.0 g (0.10 mole) of 90% t-butylhydroperoxide and the resulting solution was stirred for 5 minutes at20°-25° C. To this vigorously stirred solution at 25°-30° C. was slowlyadded a solution of 32.2 g (0.072 mole) of 93% TONE-100 chloroformate in100 mL of methyl t-butyl ether over a period of 20 minutes and theresulting reaction mass was stirred for 3 hours at 25°-32° C. Additional(50 mL) methyl t-butyl ether was added and stirring was stopped. A poorseparation of liquid phases resulted. Solid Na₂ SO₄ was added to aid theseparation of the lower aqueous layer and the upper organic layer. Thelower aqueous layer was removed and discarded. An addtional 250 mL ofmethyl t-butyl ether was added and the organic layer was washed threetimes with 100 mL portions of aqueous 20% NaOH solution, then with one100 mL portion of saturated aqueous (NH₄)₂ SO₄ solution, then theresulting mixture was allowed to settle overnight. The lower aqueouslayer was then removed and discarded. After drying over about 10% byweight of anhydrous MgSO₄ the spent desiccant was separated byfiltration and the solvent was removed in vacuo leaving 28.7 g (85% oftheory, uncorrected) of a clear viscous liquid product. The product hadan active oxygen content of 2.40% (theory, 3.40%), therefore, the assayof the product according to active oxygen content was 71% and thecorrected yield was 60%. Analysis of the product by differentialscanning calorimetry (DSC) showed a peroxide decomposition exotherm atabout 107° C.

Based on the method of preparation, yield data and DSC data the productobtained in this reaction was the desired title product, OO-t-butylO-(TONE-100) monoperoxycarbonate (PM-12): ##STR20##

EXAMPLE 13 Preparation of 2-Methacryloyloxyethyl3,3-Di-(t-butylperoxy)butyrate (PM-13)

A 500 mL jacketed reactor equipped with a mechanical stirrer, athermometer and an addition funnel was charge with 39.9 g (0.19 mole) of2-acetoacetoxyethyl methacrylate, 68.5 g (0.53 mole) of aqueous 70%t-butyl hydroperoxide solution and 7.0 g of granular ammonium sulfateand the resulting mixture was stirred for 5 minutes at room temperature.Stirring was stopped and the lower aqueous layer that formed (15.3 g)was removed and discarded. To the resulting vigorously stirred solutionat 0°-3° C. was added 56.0 g of aqueous 70% sulfuric acid solution overa period of 10-15 minutes. Then the resulting mixture was vigorouslystirred for 3 hours at 0°-3° C. At the end of the stir period a solidwas present in the reaction mass, therefore, 400 mL of methylenechloride was added in order to dissolve the solid product and to aid inthe work-up. Stirring was stopped and the resulting aqueous layer (70.5g) was removed and discarded. The stirred product layer was then treatedwith 200 mL of 5% aqueous NaOH solution at 0°-5° C. for 5 minutes. Theaqueous layer was removed and the latter wash procedure was repeated onthe product. The product solution was then washed with 50 mL portions ofwater until the pH of the product was 7. The product solution was thendried over 28.4 g of anhydrous MgSO₄ and after removal of the spentdesiccant by filtration the solvent was removed in vacuo leaving 61.3 g(86% of theory, uncorr.) of a light yellow oil which solidified onstanding at room temperature. This product was recrystallized from 1/1methanol/water and was dried. Obtained was 48.1 g (67% of theory,uncorr.) of white solid, mp, 35° C. The product had an active oxygencontent of 9.14% (theory, 8.50%), therefore, the assay of the productaccording to active oxygen content was 100% and the corrected yield was67%.

In another experiment in which the yield was considerably lower, theproduct had a melting point of 30°-5° C. and a rapid heat temperature of132° C. During the rapid heat test the sample initially melted, thensolidified before it decomposed at the rapid heat temperature. Thisobservation showed that the product, 2-methacryloyloxyethyl3,3-di-(t-butylperoxy) butyrate (PM-13), polymerized to a solid peroxypolymer prior to decomposing.

Based on the method of preparation, assay data and safetycharacteristics the product obtained from the reaction of this examplewas the desired title product, 2-methacryloyloxyethyl3,3-di-(t-butylperoxy)butyrate (PM-13).

EXAMPLE 14 Preparation ofDi-(3-methacryloyloxy-1,1-dimethylbutyl)Peroxide (PM-14)

A 125 mL Erlenmeyer flask equipped with a magnetic stirring bar and athermometer was charged with 4.7 g (0.020 mole) of 100%di-(3-hydroxy-1,1-dimethylbutyl) peroxide, 6.2 g (0.078 mole) ofpyridine and 30 mL of methyl t-butyl ether. To this solution at roomtemperature was rapidly added a solution of 4.7 g (0.040 mole) of 90%methacryloyl chloride in 20 mL of methyl t-butyl ether over a period of2 minutes. The reaction mass rapidly exothermed from 26° C. to 33° C.and a sticky white solid formed on the sides of the flask. Afterstirring for 90 minutes at room temperature the reaction mixture wasallowed to stand overnight at room temperature. Then to the stirredreaction mass was added 50 mL of water and 25 mL of methyl t-butylether, and, after allowing the mixture to settle into two liquid phases,the lower aqueous layer was removed and discarded. The product solutionwas washed twice with 50 mL portions of 1.5% aqueous hydrochloric acidsolution and then once with a 50 mL portion of saturated aqueous NaHCO₃solution. The product solution was then dried over about 10% by weightof anhydrous MgSO₄ and after removal of the spent desiccant byfiltration the solvent was removed in vacuo leaving 6.6 g (89% oftheory, uncorr.) of a yellow liquid product. An infrared spectrum of theproduct showed a slight OH band centered at ca. 3500 cm⁻¹, a strongester carbonyl band at ca. 1720 cm⁻¹, a carbon-carbon double bond bandat ca. 1640 cm⁻¹ and a small --OO-- band at ca. 870 cm⁻¹.

Based on the method of preparation, yield and infrared spectral data theproduct obtained from the reaction of this example was the desired titleproduct, di-(3-methacryloyloxy-1,1-dimethylbutyl)peroxide (PM-14).

EXAMPLE 15 Copolymerization of 1,3-Dimethyl-3-(t-butylperoxy)butylN-[1-{3-(1-Methylethenyl)phenyl}-1-methylethyl]carbamate (PM-1) withStyrene to form a Peroxy Polymer (PP-1)

Copolymerization of the peroxy monomer of Example 1 (PM-1) with styrene:

A one-liter reactor was fitted with a nitrogen inlet line, athermometer, a mechanical stirrer with a turbine impeller and a refluxcondenser. The reactor was charged with 450 g of triply distilled water,1.0 g calcium phosphate powder, and 0.75 g of polyvinyl alcohol. Theaqueous suspension was sparged with nitrogen and was heated to 80° C.Then a solution of 144.0 g (1.38 moles) of styrene, 6.0 g (15.3 mmoles)of the peroxy monomer of Example 1 (PM-1), 0.8 g (2.1 mmoles) of 50%t-amyl peroxypivalate and 0.4 g (1.7 mmoles) of 98% t-amylperoxy-2-ethylhexanoate (LUPERSOL 554-M50 and LUPERSOL 575,respectively, both manufactured by ELF ATOCHEM North America, Inc.) wasadded to the reactor. The reaction mixture was stirred between 400-600rpm at 80° C. for 2 hours and then at 90° C. for 4 hours. The reactionmixture was cooled to room temperature, acidified to a pH of 1 with20-25 mL of 10% HCl, and suction filtered. The filter cake was washedwith deionized water until a pH 6 was attained. After drying 140.9 g(93.9%) of polystyrene copolymer was obtained. An infrared spectrum ofthe product was essentially identical to one for polystyrene except thatthere was an additional peak of moderate intensity at 1730 cm⁻¹ for thecarbonyl group derived from the peroxy monomer. The molecular weightdistribution as determined by size exclusion gel permeationchromatography was as follows: Mn, 60,000; Mw, 275,000; Mz, 715,000.Analysis by high performance liquid chromatography showed that there was0.4% residual starting peroxy monomer (PM-1) present. If nocopolymerization occurred the residual peroxy monomer (PM-1) would beabout 4%. To insure that no peroxy monomer (PM-1) was present, a 7.0 gsample of the copolymer was dissolved 40 mL of xylene at 60° C. Theresultant solution was added slowly to a vigorously stirred solution ofmethanol (methanol to xylene 10:1) in order to precipitate the copolymerand to wash out any residual peroxy monomer (PM-1). The resultingcopolymer was then washed with fresh methanol and was subsequentlydried. Analysis of the precipitated and methanol washed copolymer bydifferential scanning calorimetry showed a peroxide decomposition peakwith an onset temperature of 186° C.

The above results demonstrate that a peroxy monomer of this invention(PM-1) can be copolymerized with a co-monomer to form a peroxy polymer(PP-1) and that the peroxide function is indeed chemically attached tothe peroxy copolymer (PP-1) since it was not lost by dissolving,reprecipitating and methanol washing of the resulting copolymer.

EXAMPLE 16 Terpolymerization of Methyl Methacrylate, Allyl Methacrylateand 1-(1-Isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene to form anAcrylic Terpolymer with Pendant Reactive Isocyanato Groups followed byReaction with 3-Hydroxy-1,1-dimethylbutyl Peroxy-2-ethylhexanoate toform a Peroxy Polymer (PP-2) with Pendant Peroxyester Groups

A 1.5 liter jacketed glass reactor that was fitted with a mechanicalstirrer, a thermometer, a nitrogen sparge line, a reflux condenser and amonomer feed line was charged with 340 g of methyl ethyl ketone. Thesolvent was sparged with nitrogen and was heated to 75° C. Amonomer/initiator feed consisting of 18 g (0.143 mole) of allylmethacrylate, 158.1 g of (1.58 moles) of methyl methacrylate, 69.9 g(0.269 mole) of TMI and 12.0 g (0.0346 mole) of di-(sec-butyl)peroxydicarbonate (LUPERSOL 225, manufactured by ELF ATOCHEM NorthAmerica, Inc.) was metered into the hot solvent at a rate of 5.2 g/min.During the first hour of the reaction the reaction temperature was 66°C. due to cooling caused by the monomer feed. Subsequently, thetemperature rose to 69° C. After a total reaction time of 220 minutes, a1.0 mL aliquot of the clear reaction solution was withdrawn and wasadded to pentane to precipitate the polymer. An infrared spectrum (Nujolmull) of the resulting polymer showed a strong isocyanate band at 2290cm⁻¹. To the acrylic copolymer reaction solution was added 69.6 g (0.269mole) of 3-hydroxy-1,1-dimethylbutyl peroxy-2-ethylhexanoate (LUPERSOL665, manufactured by ELF ATOCHEM North America, Inc.) and 6.0 g ofdibutyltin dilaurate. After the reaction mixture was stirred at 60° C.for 90 minutes, an additional 3.0 g of dibutyltin dilaurate was added.After another 90 minutes, an infrared spectrum of the resultant polymershowed the complete absence of the isocyanate band, showing that thependant isocyanato groups of the acrylic terpolymer had completelyreacted with 3-hydroxy-1,1-dimethylbutyl peroxy-2-ethylhexanoate to forman acrylic terpolymer (i.e., PP-2) with pendant peroxyester groups.

This example illustrated an alternate procedure for the preparation of aperoxy polymer. It also demonstrated the reaction of a suitablyfunctionalized peroxide with a polymer possessing pendant isocyanatogroups to form a peroxy polymer.

EXAMPLE 17 Copolymerization of 1,3-Dimethyl-3-(t-butylperoxy)butylAcrylate (PM-10) with Styrene to form a Peroxy Polymer (PP-3)

Copolymerization of the peroxy monomer of Example 10 (PP-10) withstyrene to form a peroxy polymer (PP-3):

The polymerization reactor employed in this example was a Parr, 2-literstirred stainless steel pressure vessel with a Model 4843 temperaturecontroller. The stirring shaft was equipped with two six-bladedstainless steel impellers positioned approximately 5 cm apart on theshaft. The stir speed was held constant at about 460 rpm.

The above reactor was charged at room temperature with 46 g of 1%aqueous Airvol™ 540 (manufactured by Air Products Corp.) solution, 2.3 gof 0.1% aqueous Emulphogene™ BC-840 (manufactured by GAF Corp.)surfactant solution, 415 g of deionized water, 266.8 g (2.56 moles) ofstyrene monomer (inhibited), 8.25 g (0.034 mole) of1,3-dimethyl-3-(t-butylperoxy)butyl acrylate (PM-10), 0.73 g of t-amylperoxypivalate and 0.62 g of2,5-dimethyl-2,5-di-(2-ethylhexanoylperoxy)hexane (LUPERSOL 256,manufactured by ELF ATOCHEM North America, Inc.). The reactor was thenpurged with nitrogen, sealed and pressurized with nitrogen to 20 psi.The time-temperature profile employed in the vigorously stirredcopolymerization reaction was as follows:

a) Warm to 70° C.

b) 70° C. for 60 minutes.

c) 75° C. for 60 minutes.

d) 90° C. for 180 minutes.

e) 95° C. for 65 minutes.

f) Cool to room temperature.

The reaction vessel was then vented and the resulting suspendedcopolymer was acidified with aqueous HCl and diluted with 150 g of icewater. The resulting polymer was separated from the aqueous slurry byfiltration and the resulting wet polymer was washed several times withwater after which the polymer beads were dried overnight on a largepaper tray. Approximately 254 g of white polymer beads was obtainedafter drying. The active oxygen content of the product peroxy copolymer(PP-3) was 0.12% (theory, 0.20%). The peroxy copolymer molecular weightswere as follows:

M_(n) --92,000

M_(w) --300,000

M_(z) --688,000

DSC showed that the product peroxy copolymer had a T_(g) of about 98° C.and a peroxide decomposition exotherm at about 201° C. An infraredspectrum of the product showed a small ester carbonyl band at about 1720cm⁻¹. Except for this band the infrared spectrum of the product peroxycopolymer was exactly the same as that of the authentic polystyrene.

The above results for the analyses of the product copolymer demonstratethat the desired title peroxy polymer (PP-3) was successfully preparedby the method of this example.

EXAMPLE 18 Crosslinking Efficiency of 1,3-Dimethyl-3-t-butylperoxy)butylN-[1-{3-(1-Methylethenyl)-phenyl}-1-methylethyl]carbamate (PM-1) in HighDensity Polyethylene (HDPE)

The appropriate amount of peroxide was compounded into high densitypolyethylene (HDPE, produced by U.S. Industrial Chemical, grade LY66000)using a Brabender Plastograph at 140° C. for 5 min. The crosslinking wasmeasured using a Monsanto Rheometer run at 385° F. and 3° arc. Employedas crosslinking peroxides were 1,3-dimethyl-3-(t-butylperoxy)butylN-[1-{3-(1-methylethenyl)phenyl}-1-methylethyl]carbamate (PM-1, a peroxymonomer of the instant invention) and two commercially employedcrosslinking peroxides, i.e., 2,5-dimethyl-2,5-di-(t-butylperoxy)hexaneand 2,5-dimethyl-2,5-di-(t-butylperoxy)-3-hexyne (LUPERSOL 101 andLUPERSOL 130, respectively, both manufactured by ELF ATOCHEM NorthAmerica, Inc.). The following crosslinking results were obtained for useof 10 meq. of peroxide per 100 g of HDPE:

    ______________________________________    Formulation     A          B      C    ______________________________________    PM-1 (phr) (Example 1)                    3.91    LUPERSOL 101 (phr)         1.45    LUPERSOL 130 (phr)                1.43    M.sub.H (in-lbs)                    62         38     45    M.sub.H -M.sub.L (in-lbs)                    60         35     44    T.sub.C90 (mins)                    4.5        4.6    8.1    T.sub.S2 (mins) 1.4        1.2    1.6    ______________________________________

The M_(H) -M_(L) results demonstrate that PM-1, the peroxy monomer ofExample 1, is an effective crosslinking agent: for HDPE when comparedwith commerically available crosslinking agents such as LUPERSOL 101 andLUPERSOL 130. Yet its use results in a reasonably short cure time(T_(C90)) and a reasonably long scorch safety time (T_(S2)).

EXAMPLE 19 Crosslinking Efficiency of1,3-Dimethyl-3-(t-butylperoxy)butyl Methacrylate (PM-9) in High DensityPolyethylene (HDPE)

1,3-Dimethyl-3-(t-butylperoxy)butyl methacrylate (PM-9) was evaluatedfor crosslinking efficiency in HDPE compared to1,3-dimethyl-3-(t-butylperoxy)butanol and2,5-dimethyl-2,5-di-(t-butylperoxy)-3-hexyne (LUPERSOL 130). PM-9,1,3-dimethyl-3-(t-butylperoxy)butanol and LUPERSOL 130, at appropriatelevels, were blended into HDPE (USI's LY66000 HDPE) at 140° C. using aBrabender mixer. Disks of the compounded HDPE resins were pressed outand these resin disks were used for determining crosslinking data usinga Monsanto Oscillating Disk Rheometer (ODR) at 385° F.,±3° arc. Thecrosslinking data obtained are summarized in the table below:

    ______________________________________    CROSSLINKING OF HDPE AT 385 deg. F. (196 deg. C.)    FORMULATION:    A      B      C     D    E    ______________________________________    LUPERSOL 130 (phr)                    1.43   --     --    --   --    1,3-Dimethyl-3- --     1.43   1.93.sup.1                                        --   --    (t-butylperoxy)-butanol (phr)    PM-9 (phr)      --     --     --    1.43 2.58.sup.1    M.sub.H (in-lbs)                    41     19.5   24.5  25   43.5    M.sub.H -M.sub.L (in-lbs)                    40     17.8   22.8  24   42.5    T.sub.C90 (mins)                    11.1   4.5    4.4   6.0  5.5    T.sub.S2 (mins) 1.85   1.45   1.35  2.3  2.0    ______________________________________     .sup.1 Level equivalent in peroxide content to LUPERSOL 130 at 1.43 phr.     .sup.2 All sample levels corrected for assay.

These data demonstrate that PM-9, a peroxy monomer of the instantinvention, is much more efficient than1,3-dimethyl-3-(t-butylperoxy)butanol and is as efficient a crosslinkingagent for HDPE as the commercial product LUPERSOL 130 when employed atan equivalent peroxide basis as judged by change in torque data. Inaddition, PM-9 gave faster cures of HDPE than the commerical productLUPERSOL 130 as judged by T_(C90) data. Finally, and surprisingly, PM-9was somewhat less scorchy than was the commerical product LUPERSOL 130as judged by T_(S2) data. Consequently, the results showed that PM-9, aperoxy monomer of the instant invention, was a very good crosslinkingperoxide candidate for HDPE.

EXAMPLE 20 Copolymerization of 1,3-Dimethyl-3-(t-butylperoxy)butylAcrylate (PM-10) with Methyl Methacrylate to form a Peroxy Polymer(PP-4)

Copolymerization of the peroxy monomer of Example 10 (PM-10) with methylmethacrylate to form a peroxy polymer (PP-4):

The polymerization reactor employed in this vessel was a Parr 2-literstirred stainless steel pressure vessel with a Model 4843 temperaturecontroller. The stirring shaft was equipped with two six-bladedstainless steel impellers positioned approximately 5 cm apart on theshaft. The stirring speed was held constant at about 470 rpm.

The above reactor was charged at room temperature with about 50g of 1%aqueous Airvol™ 540 (manufactured by Air Products Corp.) solution, 2.0 gof 0.1% aqueous Emulphogene™ BC-840 (manufactured by GAF Corp.)surfactant solution and 590 g of deionized water. Then a solution of 188g (1.88 moles of methyl methacrylate monomer, 12.0 g (0.05 mole) of1,3-dimethyl-3-(t-butylperoxy)butyl acrylate (PM-10) and 1.02 g of 98%di-(2-butyl) peroxydicarbonate (LUPERSOL 225, manufactured by ELFATOCHEM North America, Inc.) was added to the reactor. The reactor wasthen purged with nitrogen, sealed, pressurized with nitrogen to 20 psi(137.9 kPa) and stirring was started. The time temperature profile inthe vigorously stirred copolymerization reaction was as follows:

a) warm to 65° C.,

b) 65° C. for 30 minutes,

c) 70° C. for 120 minutes,

d) 75° C. for 60 minutes,

e) cool to room temperature (24° C.).

The reaction vessel was then vented and opened. To the resulting polymerslurry was added 100 g of ice and the slurry was stirred. The copolymerwas separated from the aqueous slurry by filtration and the resultingwet product was washed several times with water. The copolymer wasslurried in methanol, filtered and dried overnight on a large papertray. Approximately 190 g of white beads of the title peroxy copolymerproduct (PP-4) was obtained after drying. The active oxygen content ofthe peroxy copolymer was 0.37% (theory, 0.39%), the methyl methacrylatemonomer level was 0.21% and the peroxy monomer level was 0.09%. Theperoxy copolymer molecular weights were as follows:

M_(n) --87,600

M_(w) --320,000

M_(z) --720,000

Thermomechanical analysis (TMA) showed that the product peroxy copolymer(PP-4) had a T_(g) of about 97° C. whereas poly(methylmethacrylate) hada T_(g) of about 105° C.

The above results for the analyses of the product copolymer demonstratethat the desired title proxy copolymer (PP-4) was successfully preparedby the method of this example.

EXAMPLE 21 Preparation of 1,3-Dimethyl-3-(acetylperoxy)butylN-[1-(3-(1-Methylethenyl)phenyl)-1-methylethyl]carbamate (PM-15)##STR21## Reaction of 3-hydroxy-1,1-dimethylbutyl peroxyacetate with1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene (TMI): A200-mL 3-neck flask equipped with a magnetic stirrer, a thermoneter, anda condenser was charged with about 10 g of methyl t-butyl ether, 5.0 g(27.0 mmoles) of 94.8% 3-hydroxy-1,1-dimethylbutyl peroxyacetate, 5.0 g(25 mmoles) of TMI, and 0.1 g of dibutyltin dilaurate (catalyst). Thecontents of the flask were stirred and held at 55°-60° C. for 9 hours.An infrared spectrum of the reaction mass still showed the presence ofTMI as judged by a significant isocyanate band at cm⁻¹. The reactionmass was stirred at 25° C. for 14 hours, then at 55°-60° C. for 4 hours.An infrared spectrum of the reaction mass at this point indicated thatlittle or no TMI was present. The reaction mixture was then cooled to30° C., 5 mL of methanol was added and the reaction mixture was stirredfor 0.5 hour. As much of the solvent as was possible was removed using arotary evaporator. To the resulting paste was added 100 mL of pentane,the solid was separated by filtration and the pentane was removed usinga vacuum rotary evaporator. The solid-liquid residue was added to 100 mLof hexane, the mixture was heated to 55° C., and the hexane solution wasseparated from the solid by decantation. Hexane was removed using avacuum rotary evaporator, leaving 4.7 g (50% of theory, uncorrecned) ofa clear liquid product. A liquid chromatography scan of the productshowed that it contained 1.6% of starting 3-hydroxy-1,1-dimethylbutylperoxyacetate. The peroxyester active oxygen content of the product was3.99% (theory, 4.24%). Based on corrected peroxyester active oxygencontent, the assay of the product was 90.7% and the corrected yield was45.3%. Analysis of the product by infrared spectroscopy showed a strongcarbonyl absorption at 1725 cm⁻¹ with a shoulder at about 1770 cm⁻¹, andthe absence of an isocyanate absorption at about 2250 cm⁻¹. EXAMPLE 22Preparation of 1,3-Dimethyl-3-(isobutyrylperoxy)butylN-(1-{3-(1-Methylethenyl)phenyl}phenyl}-1-methylethyl]carbamate (PM-16)##STR22## Reaction of 3-hydroxy-1,1-dimethylbutyl peroxyisobutyrate with1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene (TMI): A200-mL 3-neck flask equipped with a magnetic stirrer, a thermometer, anda condenser was charged with about 10 g of methyl t-butyl ether, 5.9 g(27.0 mmoles) of 93.8% 3-hydroxy1,1-dimethylbutyl peroxyisobutyrate, 5.0g (25 mmoles) of TMI, and 0.1 g of dibutyltin dilaurate (catalyst). Thecontents of the flask were stirred and held at 55°-60° C. for 9 hours.An infrared spectrum of the reaction mass still showed the presence ofTMI as judged by a significant isocyanate band at 2250 cm⁻¹. Thereaction mass was stirred at 25° C. for 14 hours, then at 55°-60° C. for3 hours. An infrared spectrum of the reaction mass at this pointindicated that little or no TMI was present. The reaction mixture wasthen cooled to 35° C., 5 mL of methanol was added and the reactionmixture was stirred for 20 minutes. As much of the solvent as waspossible was removed using a rotary evaporator and the solid thatremained in the liquid was separated by filtration. To the resultingliquid was added 100 mL of pentane, the solution was cooled to 0° C. to5° C., the solid that precipitated was separated by filtration and thepentane was removed using a vacuum rotary evaporator. Obtained was 7.8 g(77% of theory, uncorrected) of a yellow liquid product. A liquidchromatography scan of the product showed that it contained 1.1% ofstarting 3-hydroxy-1,1-dimethylbutyl peroxyisobutyrate. The peroxyesteractive oxygen content of the product was 3.73% (theory, 3.95%). Based oncorrected peroxyester active oxygen content, the assay of the productwas 92.2% and the corrected yield was 71.2%. Analysis of the product byinfrared spectroscopy showed a strong carbonyl absorption at 1725 cm⁻¹and 1770 cm⁻¹, and absence of an isocyanate absorption at about 2250cm⁻¹.

The subject matter which applicants regard as their invention isparticularly pointed out and distinctly claimed as follows:

We claim:
 1. Polymeric peroxides derived from the ethylenicallyunsaturated peroxide compositions of Structure A.

    R--Q--X--R.sub.1                                           A

such polymeric peroxides possessing recurring units selected fromStructures B, C and D: ##STR23## where: Q is an unsaturated diradicalselected from structures (1), (2) or (3): ##STR24## where --(X--R₁)shows the point of attachment of the X--R₁ group and (R)--shows thepoint of attachment of the R group to the Q diradical; R is selectedfrom the group consisting of H--, carboxy, alkoxycarbonyl radicals of 2to 19 carbons, aryloxycarbonyl radicals of 7 to 15 carbons,t-alkylperoxycarbonyl radicals of 5 to 11 carbons, alkyl radicals of 1to 18 carbons, alkenyl radicals of 2 to 18 carbons, aryl radicals of 6to 10 carbons, and R₁ --X-- radicals; R₂ is selected from the groupconsisting of H-- and alkyl radicals of 1 to 4 carbons; R₃ is selectedfrom the group consisting of H--, and alkyl radicals of 1 to 18 carbonsand alkenyl radicals of 2 to 18 carbons, provided that when R₃ ismethyl, R and R₂ are not both hydrogen; R₁ is a peroxy-containingradical of structures (4), (5) and (6): ##STR25## where t is 0 or 1; vis 1 or 2; w is 1 or 2; T is a direct bond or oxy; R₄ is selected fromthe group consisting of t-alkyl radicals of 4 to 12 carbons, t-aralkylradicals of 9 to 13 carbons and t-alkynyl radicals of 5 to 9 carbons;R₅, R₈ and R₉ are the same or different and are selected from the groupconsisting of alkyl radicals of 1 to 4 carbons; in structure (5) andwhen T is a direct bond is structure (6), R₆ and R₇ are the same ordifferent and are selected from the group consisting of H-- and alkylradicals of 1 to 4 carbons; in structure (6) when T is oxy, R₆ and R₇are the same or different and are selected from the group consisting ofalkyl radicals of 1 to 4 carbons; R₁₀ is selected from the groupconsisting of t-alkyl radicals of 4 to 12 carbons, t-aralkyl radicals of9 to 13 carbons, t-alkynyl radicals of 5 to 9 carbons, and structures(7), (8), (9), (10), (11) and (12): ##STR26## where: R₁₂ and R₁₃ can bethe same or different and are selected from the group consisting of H--and alkyl radicals of 1 to 8 carbons; R₁₄ is selected from the groupconsisting of H--, alkyl radicals of 1 to 8 carbons, alkenyl radicals of2 to 8 carbons, aryl radicals of 6 to 10 carbons, alkyoxy radicals of 1to 6 carbons and aryloxy radicals of 6 to 10 carbons; R₁₃ and R₁₄ may beconcatenated to form an alkylene diradical of 4 to 5 carbons; R₁₅ andR₁₆ are independently selected from alkyl radicals of 1 to 4 carbons;R₁₇ and R'₁₇ are independently selected from the group consisting ofH--, lower alkyl radicals of 1 to 4 carbons, alkoxy radicals of 1 to 4carbons, phenyl radicals, acyloxy radicals of 2 to 8 carbons,t-alkylperoxycarbonyl radicals of 5 to 9 carbons, hydroxy, fluoro,chloro, and bromo; x is 0 or 1; R₁₈ is selected from substituted orunsubstituted alkyl radicals of 1 to 18 carbons, substituted orunsubstituted cycloalkyl radicals of 5 to 12 carbons, substituted orunsubstituted heterocyclic radicals having an oxygen atom or a nitrogenatom in the heterocyclic ring, with substituents for the alkyl radicalsbeing one or more alkyl radicals of 1 to 6 carbons, t-alkylperoxyradicals of 4 to 8 carbons, alkoxy radicals of 1 to 6 carbons, aryloxyradicals of 6 to 10 carbons, hydroxy, chloro, bromo and cyano and withsubstituents for either cyclic radical being one or more lower alkylradicals of 1 to 4 carbons, or R₁₈ is the radical: ##STR27## where y is0 or 1, R_(a), R_(b) and R_(c) are the same or different and areselected from H-- or alkyl radicals of 1 to 8 carbons, with the provisothat R_(a) and R_(b) may be concatenated to form a substituted orunsubstituted alkylene diradical of 4 to 11 carbons, substituents beingone or more alkyl radicals of 1 to 5 carbons or phenyl radicals; R₁₉ isselected from the group consisting of alkyl radicals of 1 to 4 carbonsand, additionally, the two R₁₉ radicals may optionally be concatenatedto form an alkylene diradical of 4 to 5 carbons; R₁₁ is selected fromthe group consisting of unsubstituted alkylene diradicals of 2 to 3carbons, alkylene diradicals of 2 to 3 carbons substituted with one ormore lower alkyl radicals of 1 to 4 carbons, a 1,2-phenylene diradical,1,2-phenylene diradicals substituted with one or more lower alkylradicals of 1 to 4 carbons, chloro, bromo, nitro or carboxy; and, X is adirect bond or is selected from the group consisting of connectingdiradical structures (13) , (14) , (15) and (16): ##STR28## where (R--Q)shows the point of attachment of the R--Q group to the unsymmetrical Xconnecting diradical; z is 1 to 10; R₂₂ is an alkylene diradical of 2 to4 carbons, optionally substituted with one or more alkyl radicals of 1to 4 carbons; and when the X connecting diradical is structure (16), R₁may additionally be the peroxide containing radical of the structure(17) ##STR29##
 2. A polymeric peroxide as defined in claim 1 wherein theunsaturated peroxide of Structure A is selected from the groupconsisting of:1,3-Dimethyl-3-(t-butylperoxy)butylN-[1-{3-(1-methylethyl)phenyl]-1-methylethyl]carbamate,3-methyl-3-(t-butylperoxy)butylN-[1-{3-(1-methylethenyl)phenyl}-1-methylethyl]carbamate,di-[1,1-dimethyl-3-(1-{3-(1-methylethenyl)}phenyl-1-methylethylaminocarbonyloxy)butyl]peroxide,1,3-dimethyl-3-(2-methylbenzoylperoxy)butylN-[1-{3-(1-methylethenyl)phenyl}-1-methylethyl]carbamate,1,3-dimethyl-3-(acetylperoxy)butylN-[1-{3-(1-methylethenyl)phenyl}-1-methylethyl]carbamate,1,3-dimethyl-3-(isobutyrylperoxy)butylN-[1-{3-(1-methylethenyl)phenyl}-1-methylethyl]carbamate,1,3-dimethyl-3-(t-amylperoxy)butylN-[1-{3-(t-methylethenyl)phenyl}-1-methylethyl]carbamate, ethyl1,3-dimethyl-3-(t-butylperoxy)butyl fumarate,di-[1,3-dimethyl-3-(t-butylperoxy)butyl]fumarate,1,3-dimethyl-3-(t-butylperoxy)butyl hydrogen maleate,1,3-dimethyl-3-(t-butylperoxy)butyl methacrylate,1,3-dimethyl-3-(t-butylperoxy)butyl acrylate,1,3-dimethyl-3-(t-butylperoxy)butyl TONE-100 carbonate, OO-t-butylO-(TONE-100) monoperoxycarbonate, 2-methacryloyloxyethyl3,3-di-(t-butylperoxy)butyrate and di(3-methacryloyloxy-1,1-dimethylbutyl)peroxide.
 3. A polymeric peroxideas defined in claim 1 wherein X is the unsaturated peroxide compositionin structure (13) as defined as claim
 1. 4. A polymeric peroxide asdefined in claim 1 wherein X, in the unsaturated peroxide composition isa direct bond.
 5. A polymeric peroxide as defined in claim 1 wherein Xin the unsaturated peroxide composition is structure (16).
 6. Apolymeric peroxide as defined in claim 1 wherein X in the unsaturatedperoxide composition is structure (15).
 7. A polymeric peroxide asdefined in claim 1 wherein R₁ in the unsaturated peroxide composition isstructure (5).
 8. A polymeric peroxide as defined in claim 1 wherein R₁in the unsaturated peroxide composition is structure (17).
 9. Apolymeric peroxide as defined in claim 1 wherein R₁ in the unsaturatedperoxide composition is structure (4).
 10. A polymeric peroxide asdefined in claim 1 wherein in the unsaturated peroxide composition isstructure (12).
 11. A polymeric peroxide as defined in claim 1 wherein Qin the unsaturated peroxide composition is structure (1) wherein R, R₂and R₃ are H--.
 12. A polymeric peroxide as defined in claim 1 wherein Qin the unsaturated peroxide composition is structure (1) wherein R isalkoxycarbonyl, R₂ and R₃ are H--.
 13. A polymeric peroxide as definedin claim 1 wherein Q in the unsaturated peroxide composition isstructure (3) wherein R is H--.
 14. A polymeric peroxide as defined inclaim 1 wherein Q in the unsaturated peroxide composition is structure(1) wherein R is R₁ --X--, R₂ and R₃ are H--.